Supported group 8-10 transition metal olefin polymerization catalysts

ABSTRACT

Methods for preparing olefin polymers, and catalysts for preparing olefin polymers are disclosed. The polymers can be prepared by contacting the corresponding monomers with a Group 8-10 transition metal catalyst and a solid support. The polymers are suitable for processing in conventional extrusion processes, and can be formed into high barrier sheets or films, or low molecular weight resins for use in synthetic waxes in wax coatings or as emulsions.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation of application Ser. No. 09/579,793, filed May 26,2000, now Pat. No. 6,660,677, which is a continuation-in-part ofapplication Ser. No. 09/177,099, filed Oct. 22, 1998, now U.S. Pat. No.6,103,658, which claims the benefit under 35 U.S.C. 119(e) ofProvisional Application No. 60/062,609, filed Oct. 22, 1997, and whichis a continuation-in-part of application Ser. No. 09/088,223, filed Jun.1, 1998, now abandoned; which is a continuation-in-part of applicationNo. 09/030,058, filed Feb. 24, 1998, now abandoned; which claims thebenefit under 35 U.S.C. 119(e) of Provisional Application No.60/040,363, filed Mar. 10, 1997, Provisional Application No. 60/041,542,filed Mar. 25, 1997; Provisional Application No. 60/042,925, filed Apr.4, 1997, Provisional Application No. 60/043,406, filed Apr. 4, 1997,Provisional Application No. 60/044,691, filed Apr. 18, 1997; andProvisional Application No. 60/059,372, filed Sep. 18, 1997; all ofwhich are incorporated by reference.

BACKGROUND OF THE INVENTION

The present invention is directed to Group 8-10 transitionmetal-containing complexes, their use in olefin polymerizations, and tonovel olefin polymers produced thereby.

Olefin polymers are used in a wide variety of products, from sheathingfor wire and cable to film. Olefin polymers are used, for instance, ininjection or compression molding applications, in extruded films orsheeting, as extrusion coatings on paper, for example photographic paperand digital recording paper, and the like. Improvements in catalystshave made it possible to better control polymerization processes, and,thus, influence the properties of the bulk material. Increasingly,efforts are being made to tune the physical properties of plastics forlightness, strength, resistance to corrosion, permeability, opticalproperties, and the like, for particular uses. Chain length, polymerbranching and functionality have a significant impact on the physicalproperties of the polymer. Accordingly, novel catalysts are constantlybeing sought in attempts to obtain a catalytic process for polymerizingolefins which permits more efficient and better controlledpolymerization of olefins.

Conventional polyolefins are prepared by a variety of polymerizationtechniques, including homogeneous liquid phase, gas phase, and slurrypolymerization. Certain transition metal catalysts, such as those basedon titanium compounds (e.g. TiCl₃ or TiCl₄) in combination withorganoaluminum cocatalysts, are used to make linear and linear lowdensity polyethylenes as well as poly-α-olefins such as polypropylene.These so-called “Ziegler-Natta” catalysts are quite sensitive to oxygenand are ineffective for the copolymerization of nonpolar and polarmonomers.

Recent advances in non-Ziegler-Natta olefin polymerization catalysisinclude the following.

L. K. Johnson et al., WO Patent Application 96/23010, disclose thepolymerization of olefins using cationic nickel, palladium, iron, andcobalt complexes containing diimine and bisoxazoline ligands. Thisdocument also describes the polymerization of ethylene, acyclic olefins,and/or selected cyclic olefins and optionally selected unsaturated acidsor esters such as acrylic acid or alkyl acrylates to provide olefinhomopolymers or copolymers.

European Patent Application Serial No. 381,495 describes thepolymerization of olefins using palladium and nickel catalysts whichcontain selected bidentate phosphorous containing ligands.

L. K. Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414, describe thepolymerization of olefins such as ethylene, propylene, and 1-hexeneusing cationic α-diimine-based nickel and palladium complexes. Thesecatalysts have been described to polymerize ethylene to high molecularweight branched polyethylene. In addition to ethylene, Pd complexes actas catalysts for the polymerization and copolymerization of olefins andmethyl acrylate.

G. F. Schmidt et al., J. Am. Chem. Soc. 1985, 107, 1443, describe acobalt(III) cyclopentadienyl catalytic system having the structure[C₅Me₅(L)CoCH₂CH₂-μ-H]⁺, which provides for the “living” polymerizationof ethylene.

M. Brookhart et al., Macromolecules 1995, 28, 5378, disclose using such“living” catalysts in the synthesis of end-functionalized polyethylenehomopolymers.

U. Klabunde, U.S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606, and5,175,326, describes the conversion of ethylene to polyethylene usinganionic phosphorous, oxygen donors ligated to Ni(II). The polymerizationreactions were run between 25 and 100° C. with modest yields, producinglinear polyethylene having a weight-average molecular weight rangingbetween 8K and 350 K. In addition, Klabunde describes the preparation ofcopolymers of ethylene and functional group containing monomers.

M. Peuckert et al., Organomet. 1983, 2(5), 594, disclose theoligomerization of ethylene using phosphine, carboxylate donors ligatedto Ni(II), which showed modest catalytic activity (0.14 to 1.83 TO/s).The oligomerizations were carried out at 60 to 95° C. and 10 to 80 barethylene in toluene, to produce α-olefins.

R. E. Murray, U.S. Pat. Nos. 4,689,437 and 4,716,138, describes theoligomerization of ethylene using phosphine, sulfonate donors ligated toNi(II). These complexes show catalyst activities approximately 15 timesgreater than those reported with phosphine, carboxylate analogs.

W. Keim et al., Angew. Chem. Int. Ed. Eng. 1981, 20,116, and V. M.Mohring, et al., Angew. Chem. Int. Ed. Eng. 1985, 24, 1001, disclose thepolymerization of ethylene and the oligomerization of α-olefins withaminobis(imino)phosphorane nickel catalysts; G. Wilke, Angew. Chem. Int.Ed. Engl. 1988, 27, 185, describes a nickel allyl phosphine complex forthe polymerization of ethylene.

K. A. O. Starzewski et al., Angew. Chem. Int. Ed. Engl. 1987, 26, 63,and U.S. Pat. No. 4,691,036, describe a series of bis(ylide) nickelcomplexes, used to polymerize ethylene to provide high molecular weightlinear polyethylene.

WO Patent Application 97/02298 discloses the polymerization of olefinsusing a variety of neutral N, O, P, or S donor ligands, in combinationwith a nickel(0) compound and an acid.

Brown et al., WO 97/17380, describes the use of Pd α-diimine catalystsfor the polymerization of olefins including ethylene in the presence ofair and moisture.

Fink et al., U.S. Pat. No., 4,724,273, have described the polymerizationof α-olefins using aminobis(imino)phosphorane nickel catalysts and thecompositions of the resulting poly(α-olefins).

Recently Vaughan et al. WO 9748736, Denton et al. WO 9748742, andSugimura et al. WO 9738024 have described the polymerization of ethyleneusing silica supported α-diimine nickel catalysts.

Additional recent developments are described by Sugimura et al., inJP96-84344, JP96-84343, by Yorisue et al., in JP96-70332, by Canich etal. WO 9748735, McLain et al. WO 9803559, Weinberg et al. WO 9803521 andby Matsunaga et al. WO 9748737.

Notwithstanding these advances in non-Ziegler-Natta catalysis, thereremains a need for efficient and effective Group 8-10 transition metalcatalysts for effecting polymerization of olefins. In addition, there isa need for novel methods of polymerizing olefins employing sucheffective Group 8-10 transition metal catalysts. In particular, thereremains a need for Group 8-10 transition metal olefin polymerizationcatalysts with both improved temperature stability and functional groupcompatibility. Further, there remains a need for a method ofpolymerizing olefins utilizing effective Group 8-10 transition metalcatalysts in combination with a Lewis acid so as to obtain a catalystthat is more active and more selective.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a plot of weight fraction and cumulative weight fractionversus temperature in degree Celsius for four samples of polyethylene.

The following general procedure was used to generate this plot:

This data was collected using a polymics™ CAP-TREF (Temperature RisingElution Fractionation) system, by first preparing a one percent polymersolution in 1,2,4-trichlorobenzene. The samples were dissolved at 150°C. over two hours. An appropriate amount of CHROMASORB™ P was added tothe solution, placed in a temperature-controlled oven and cooled at arate of 2° C. per hour from 150° C. to 30° C. The TREF analysis wasperformed by heating the material at 200° C. per hour at a solvent(1,2,4-trichlorobenzene) flow rate of 20 mL per minute.

The weight fraction was determined by percent transmittance of aninfrared beam of light (3.41 μm).

Curve 1 is the weight fraction as a function of temperature of apolyethylene made in solution using the catalyst XXVII, at 80° C. and600 psig (ethylene), as per Example 196. Average branching of 45branches/1000 carbon atoms, as determined by ¹H NMR.

Curve 2 is the weight fraction as a function of temperature of apolyethylene made in solution using the catalyst XXVII, at 80° C. and600 psig (ethylene), as per Example 197. Average branching of 45branches/1000 carbon atoms, as determined by ¹H NMR.

Curve 3 is the weight fraction as a function of temperature of apolyethylene made in the gas phase using the silica-supported catalystXXVII, at 100° C. and 100 psig (ethylene), as per Example 136. Averagebranching of 45 branches/1000 carbon atoms, as determined by ¹H NMR.

Curve 4 is the weight fraction as a function of temperature of apolyethylene made in the gas phase using the silica-supported catalystXXVII, at 100° C. and 100 psig (ethylene), as per Example 150. Averagebranching of 47 branches/1000 carbon atoms, as determined by ¹H NMR.

Curve 1 a is the cumulative weight fraction as a function of temperaturefor a polyethylene prepared in solution using the catalyst XXVII, at 80°C. and 600 psig (ethylene), as per Example 196. Average branching of 45branches/1000 carbon atoms, as determined by ¹H NMR.

Curve 2 a is the cumulative weight fraction as a function of temperaturefor a polyethylene prepared in solution using the catalyst XXVII, at 80°C. and 600 psig (ethylene), as per Example 197. Average branching of 45branches/1000 carbon atoms, as determined by ¹H NMR.

Curve 3 a is the cumulative weight fraction as a function of temperaturefor a polyethylene prepared in gas phase using the silica-supportedcatalyst XXVII, at 100° C. and 100 psig (ethylene), as per Example 136.Average branching of 45 branches/1000 carbon atoms, as determined by ¹HNMR.

Curve 4 a is the cumulative weight fraction as a function of temperaturefor a polyethylene prepared in gas phase using the silica-supportedcatalyst XXVII, at 100° C. and 100 psig (ethylene), as per Example 150.Average branching of 47 branches/1000 carbon atoms, as determined by ¹HNMR.

FIG. 1 illustrates the unique compositions prepared in the gas phaseusing supported catalysts of the present invention. The polymersprepared using a homogeneous catalyst in solution (i.e., 1 and 2)dissolve over a relatively narrow temperature range, while thoseprepared using a supported catalyst in the gas phase (i.e., 3 and 4)dissolve over a much wider temperature range. Thus, the comparison ofcurves 1 and 2 versus curves 3 and 4 indicates the existence of a narrowcomposition distribution range for the polyethylenes made in solution,in sharp contrast to the polyethylenes prepared using gas phasepolymerization while using the same transition metal complex whenattached to a solid support. As can be seen in FIG. 1, curves 3 and 4depict dissolution over a much larger temperature range, evidence of amuch broader composition distribution.

In this regard, such polymer compositions provide a unique blend ofproperties, i.e., a balance of impact, toughness, elasticity,tear-resistance, and puncture resistance, which are particularly desiredfor such end uses as film, packaging, sheeting, etc.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the present invention provides a catalyst for thepolymerization of olefins comprising a complex comprising (a) a ligandof the formula X, (b) a group 8-10 transition metal, and optionally (c)a Bronsted or Lewis acid,

R¹ and R⁶ are each, independently, hydrocarbyl, substituted hydrocarbyl,or silyl; N represents nitrogen; and

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group; wherein the complexis attached to a solid support, and wherein the solid support, theoptional Bronsted or Lewis acid, and the complex are combined in anyorder to form said catalyst.

In the above catalyst, it should be appreciated that the Group 8-10transition metal has coordinated thereto a bidentate ligand having theformula X and that the Bronsted or Lewis acid is optionally reacted withthis metal-ligand complex. In addition, the Bronsted or Lewis acid maybe optionally combined with the ligand X prior to complexation to theGroup 8-10 transition metal.

In one embodiment, the invention provides a catalyst for thepolymerization of olefins comprising the reaction product of a compoundof formula XII, a compound Y and a solid support:

R¹ and R⁶ each, independently, represent hydrocarbyl, substitutedhydrocarbyl, or silyl;

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group;

Q represents an alkyl, chloride, iodide or bromide;

W represents an alkyl, chloride, iodide or bromide;

N represents nitrogen; and

M represents Ni(II), Pd(II), Co(II), or Fe(II);

and Y is selected from the group consisting of a neutral Lewis acidcapable of abstracting Q⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

As a further aspect of the invention, there is provided a process forthe preparation of supported catalysts comprising contacting a group8-10 transition metal complex of a ligand of the formula X, a solidsupport, and optionally a Bronsted or Lewis acid,

wherein R¹ and R⁶ are each, independently, hydrocarbyl, substitutedhydrocarbyl, or silyl; N represents nitrogen; and

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group; wherein the complexis attached to a solid support, and wherein the solid support, theoptional Bronsted or Lewis acid, and the complex are combined in anyorder to form said supported catalyst.

In a further embodiment, there is provided a process for the preparationof supported catalysts comprising the reaction product of a compound offormula XII, a compound Y and a solid support:

R¹ and R⁶ each, independently, represent hydrocarbyl, substitutedhydrocarbyl, or silyl;

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group;

Q represents an alkyl, chloride, iodide or bromide;

W represents an alkyl, chloride, iodide or bromide;

N represents nitrogen; and

M represents Ni(II), Pd(II), Co(II), or Fe(II);

and Y is selected from the group consisting of a neutral Lewis acidcapable of abstracting Q⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

In a further embodiment, there is provided a process for thepolymerization of olefins, comprising contacting one or more monomers ofthe formula RCH═CHR⁸ with a catalyst comprising a group 8-10 transitionmetal complex of a ligand of the formula X and optionally a Bronsted orLewis acid,

wherein R and R⁸ each, independently, represent a hydrogen, ahydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclicolefin;

R¹ and R⁶ are each, independently, hydrocarbyl, substituted hydrocarbyl,or silyl; N represents nitrogen; and

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group; wherein the complexis attached to a solid support, and wherein the solid support, theoptional Bronsted or Lewis acid, and the complex are combined in anyorder.

In a further embodiment, the present invention provides a process forthe polymerization of olefins, comprising contacting one or moremonomers of the formula RCH═CHR⁸ with the reaction product of a compoundof formula XII, a compound Y and a solid support:

wherein R and R⁸ each, independently, represent a hydrogen, ahydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclicolefin;

R¹ and R⁶ each, independently, represent hydrocarbyl, substitutedhydrocarbyl, or silyl;

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group;

Q represents an alkyl, chloride, iodide or bromide;

W represents an alkyl, chloride, iodide or bromide;

N represents nitrogen; and

M represents Ni(II), Pd(II), Co(II), or Fe(II);

and Y is selected from the group consisting of a neutral Lewis acidcapable of abstracting Q⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

In a further embodiment, the present invention provides a process forthe polymerization of olefins, comprising contacting one or moremonomers of the formula RCH═CHR⁸ with a supported catalyst formed bycombining a compound of formula XII:

with a solid support which has been pre-treated with a compound Y,

wherein R and R⁸ each, independently, represent a hydrogen, ahydrocarbyl, or a fluoroalkyl, and may be linked to form a cyclicolefin;

R¹ and R⁶ each, independently, represent hydrocarbyl, substitutedhydrocarbyl, or silyl;

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group;

Q represents an alkyl, chloride, iodide or bromide;

W represents an alkyl, chloride, iodide or bromide;

N represents nitrogen; and

M represents Ni(II), Pd(II), Co(II), or Fe(II);

and Y is selected from the group consisting of a neutral Lewis acidcapable of abstracting Q⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

In a further embodiment, a process for the copolymerization of one ormore olefin monomers of the type RCH═CHR⁸ with one or more functionalolefin monomers of the formula CH₂═CH(CH₂)_(n)J comprising a catalyst,in an olefin polymerization reaction which comprises combining a complexof the formula XII, a solid support, and optionally a compound Y, priorto the utilization of said catalyst in said olefin polymerizationreaction.

R and R⁸ each, independently, represent a hydrogen, a hydrocarbyl, or afluoroalkyl, and may be linked to form a cyclic olefin;

n is an interger between 1-20;

J is a group selected from ester, acyl, acid halide, aldehyde, alkylamide, aryl, alkylamine, aryl amine, alkyl amido, aryl amido, alkylimido, aryl imido, ether, nitrile, alcohol, keto, amino, amido, imido,alkoxy thiol, thioalkoxy, acid, urea, sulfonamido, and sulfoester;

R¹ and R⁶ each, independently, represent hydrocarbyl, substitutedhydrocarbyl, or silyl;

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group;

Q represents an alkyl, chloride, iodide or bromide;

W represents an alkyl, chloride, iodide or bromide;

N represents nitrogen; and

M represents Ni(II), Pd(II), Co(II), or Fe(II);

and Y is selected from the group consisting of a neutral Lewis acidcapable of abstracting Q⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

In a further preferred embodiment, the present invention provides aprocess for the copolymerization of ethylene and a comonomer of theformula CH₂═CH(CH₂)_(n)CO₂R¹ which comprises contacting ethylene and acomonomer of the formula CH₂═CH(CH₂)_(n)CO₂R¹ with a supported catalystformed by combining silica with a compound of the formula XII andoptionally a compound Y;

wherein R¹ is hydrogen, hydrocarbyl, substituted hydrocarbyl,fluoroalkyl or silyl;

n is an integer greater than 3;

R¹ and R⁶ each, independently, represent hydrocarbyl, substitutedhydrocarbyl, or silyl;

A and B are each, independently, a heteroatom connected mono-radicalwherein the connected heteroatom is selected from Group 15 or 16; inaddition, A and B may be linked by a bridging group;

Q represents an alkyl, chloride, iodide or bromide;

W represents an alkyl, chloride, iodide or bromide;

N represents nitrogen; and

M represents Ni(II), Pd(II), Co(II), or Fe(II);

and Y is selected from the group consisting of a neutral Lewis acidcapable of abstracting Q⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

In a further preferred embodiment, there is provided the above processwherein the compound of formula XII is substituted for the compoundrepresented by formula XXIV.

wherein R² and R³ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or silyl, or may collectively form a bridginghydrocarbyl, bridging substituted hydrocarbyl, or a substituted siliconatom;

Q is alkyl, chloride, iodide or bromide;

W is alkyl, chloride, iodide or bromide;

N is nitrogen;

Z is sulfur or oxygen; and

M is Ni(II).

In a further preferred embodiment, there is provided a supportedcatalyst comprising the reaction product of a compound of formula V,VIII, or XV:

wherein R¹ and R⁶ each, independently, represent a sterically hinderedaryl;

R², R³ and R⁴ each, independently, represent a hydrogen, hydrocarbyl,substituted hydrocarbyl, or silyl, and, in addition, may collectivelyform a bridging hydrocarbyl, bridging substituted hydrocarbyl, or asubstituted silicon atom;

Q represents a hydrocarbyl, chloride, iodide or bromide;

W represents a hydrocarbyl, chloride, iodide or bromide;

N represents nitrogen; and

M represents Ni(II), Pd(II), Co(II), or Fe(II);

with a solid support which has been pre-treated with a compound Y,wherein Y is selected from the group consisting of a neutral Lewis acidcapable of abstracting Q⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

In an especially preferred embodiment, the compound of formula XII isselected from the group consisting of

wherein R¹ and R⁶ are 2,6-dimethylphenyl;

wherein R¹ and R⁶ are 2,6-diisopropylphenyl;

wherein R¹ and R⁶ are 2,6-dimethylphenyl;

wherein R¹ and R⁶ are 2,6-diisopropylphenyl;

wherein R¹ and R⁶ are 2,6-dimethylphenyl; and

wherein R¹ and R⁶ are 2,6-diisopropylphenyl.

The catalysts used in the processes of the present invention readilyconvert ethylene and α-olefins to high molecular weight polymers, andallow for olefin polymerizations under various conditions, includingambient temperature and pressure, including gas phase and slurry (e.g.,slurry loop).

As noted herein, it is preferred that the compounds of the presentinvention be attached to a solid support which has been pretreated witha compound Y, for example, MAO, or mixed with Y in any order. We havediscovered that when such supported catalysts are used in slurry and gasphase ethylene polymerizations, novel polymer compositions are providedinsofar as such compositions are blends of different polyolefinpolymers. It is believed that when such catalysts are attached to asolid support, such as silica, olefin polymerizations using suchsupported catalysts provide a polymer composition which possesses abroad compositional distribution. This is believed to be due at least inpart to both the creation of unique reaction sites, and the sensitivityof these catalysts to ethylene concentration. These unique reactionsites are believed to result from the unique microenvironments createdby the location of the catalyst on the support. The resulting polymercomposition, which can be prepared solely from ethylene as an olefinfeedstock, is one which is actually a blend or plurality of polymershaving a variety of alkyl branched distributions with some catalystsites giving less branched high density polymer and other sites givingmore branched lower density polymer.

The present invention also provides novel polyalkene compositions. Thus,in one embodiment, the present invention provides polyethylenecomposition comprising a blend of polyethylene polymers, wherein saidblend has an average degree of branching of from 5 to 120 alkyl branchesper 1000 carbon atoms, wherein any individual component of said blendhas a degree of branching of from 0 to 150 alkyl branches per 1000carbon atoms, wherein said polymers are prepared in one reaction vessel,solely from ethylene, and wherein said polymers are prepared utilizing aGroup 8-10 transition metal catalyst supported on a solid support whichhas been pre-treated with a compound Y selected from the groupconsisting of methylaluminoxane and other aluminum sesquioxides havingthe formulas R⁷ ₃Al, R⁷ ₂AlCl, and R⁷AlCl₂ wherein R⁷ is alkyl. Thetransition metal is preferably Ni and the compound Y ismethylaluminoxane

A further embodiment of the invention provides a polyethylenecomposition comprising a blend of polyethylene polymers, wherein saidblend has an average degree of branching from 5 to 120 alkyl branchesper 1000 carbon atoms, wherein any individual component of said blendhas a degree of branching of from 0 to 150 alkyl branches per 1000carbon atoms, wherein said polymers are prepared in one reaction vessel,solely from ethylene, and wherein said polymers are prepared utilizing aGroup 8-10 transition metal catalyst which has been reacted with a solidsupport and a compound Y, in any order, wherein Y is selected from thegroup consisting of methylaluminoxane and other aluminum sesquioxideshaving the formulas R⁷ ₃Al, R⁷ ₂AlCl, and R⁷AlCl₂, wherein R⁷ is alkyl.

Further, the catalysts of this invention when supported in this fashionand utilized in a gas or slurry phase process provide polymers having abroad composition distribution while having an intermediate molecularweight distribution, thus providing certain processing advantages. Whenfractionated based on solubility using supercritical propane byisothermal increasing profiling and critical, isobaric, temperaturerising elution fractionation, into ten fractions, an analysis of suchfractions provides data on the distribution of the relative branching ofthe components of said composition.

Thus, in a further embodiment, there is provided a polyolefin which whenfractionated based on solubility using supercritical propane byisothermal increasing profiling and critical, isobaric, temperaturerising elution fractionation, into ten fractions between about 40 andabout 140° C., wherein a first fraction taken at about 40° C. hasbetween about 40 and about 100 branches per 1000 carbon atoms, whereinbetween about 50 to about 90% are methyl branches, about 5 to about 15%are ethyl branches, about 1 to about 10% are propyl branches, about 0 toabout 15% are butyl branches, and between about 5 and about 15% arepentyl or longer branches; a second fraction taken between about 40-60°C. has between about 30 and about 90 branches per 1000 carbon atoms,wherein between about 50 to about 90% are methyl branches, about 5 toabout 15% are ethyl branches, about 1 to about 10% are propyl branches,about 0 to about 15% are butyl branches, and between about 5 and about15% are pentyl or 20 longer branches; a third fraction taken betweenabout 60-65° C. has between about 30 and about 80 branches per 1000carbon atoms, wherein between about 50 to about 90% are methyl branches,about 5 to about 15% are ethyl branches, about 1 to about 10% are propylbranches, about 0 to about 15% are butyl branches, and between about 5to about 15% are 25 pentyl or longer branches; a fourth fraction takenbetween about 65-70° C. has between about 20 and about 60 branches per1000 carbon atoms, wherein between about 50 to about 90% are methylbranches, about 5 to about 15% are ethyl branches, about 1 to about 10%are propyl branches, about 0 to about 15% are butyl branches, andbetween about 5 to about 15% are pentyl or longer branches; a fifthfraction taken between about 75-85° C. has between about 10 and about 50branches per 1000 carbon atoms, wherein between about 50 to about 90%are methyl branches, about 5 to about 15% are ethyl branches, about 0 toabout 10% are propyl branches, about 0 to about 15% are butyl branches,and between about 5 to about 15% are pentyl or longer branches; a sixthfraction taken between about 85-95° C. has between about 10 and about 40branches per 1000 carbon atoms, wherein between about 50 to about 90%are methyl branches, about 5 to about 15% are ethyl branches, about 0 toabout 10% are propyl branches, about 0 to about 15% are butyl branches,and between about 5 and about 15% are pentyl or longer branches; aseventh fraction taken between about 95-100° C. has between about 5 andabout 35 branches per 1000 carbon atoms, wherein between about 50 toabout 90% are methyl branches, about 5 to about 15% are ethyl branches,about 0 to about 10% are propyl branches, about 0 to about 15% are butylbranches, and between about 0 and about 15% are pentyl or longerbranches; an eighth fraction taken between about 100-110° C. has betweenabout 0 and about 25 branches per 1000 carbon atoms, wherein betweenabout 50 to about 90% are methyl branches, about 5 to about 15% areethyl branches, about 0 to about 10% are propyl branches, about 0 toabout 15% are butyl branches, and between about 0 and about 15% arepentyl or longer branches; a ninth fraction taken between about 110-140°C. has between about 0 and about 30 branches per 1000 carbon atoms,wherein between about 50 to about 90% are methyl branches, about 5 toabout 15% are ethyl branches, about 0 to about 10% are propyl branches,about 0 to about 15% are butyl branches, and between about 0 to about15% are pentyl or longer branches; a tenth fraction taken between about140-150° C. has between about 0 and about 20 branches per 1000 carbonatoms, wherein between about 50 to about 90% are methyl branches, about5 to about 15% are ethyl branches, about 0 to about 10% are propylbranches, about 0 to about 15% are butyl branches, and between about 0to about 15% are pentyl or longer branches; and a tenth fraction hasbetween about 0 and about 20 branches per 1000 carbon atoms.

In contrast to a polymer prepared by solution polymerization, where themelting temperature as defined by the endothermic maximum is inverselycorrelated with the average degree of branching of said polymer, thepolymers prepared from the supported catalysts of the present inventionexhibit a relatively constant melting temperature (endothermic maximum)over a relatively wide range of average branching. In certain cases,this also provides a free flowing powder which is again, a significantprocessing advantage in the gas phase.

In a further embodiment, there is provided a polymer derived fromessentially ethylene alone that has greater than 30 branches per 1000carbon atoms and a melt transition (endothermic maximum) in the DSC ofgreater than about 110° C. Preferably, the polymer is a free flowingpolymer.

In a further embodiment, there is provided a polymer derived fromethylene alone that has a broad composition distribution and a molecularweight distribution of less than 6 and greater than 2.5, wherein saidpolymer has an average degree of branching of from 5 to 120 alkylbranches per 1000 carbon atoms, and wherein any individual component ofsaid polymer has a degree of branching of from 0 to 150 alkyl branchesper 1000 carbon atoms. In such polymer compositions, it is preferredthat an individual component of the polymer has between about 40 and 100branches per 1000 carbon atoms, another component has between about 30and 90 branches per 1000 carbon atoms, another component has betweenabout 30 and 80 branches per 1000 carbon atoms, another component hasbetween about 20 and 60 branches per 1000 carbon atoms, anothercomponent has between about 10 and 50 branches per 1000 carbon atoms,another component has between about 10 and 40 branches per 1000 carbonatoms, another component has between about 5 and 35 branches per 1000carbon atoms, another component has between about 0 and 25 branches per1000 carbon atoms, another component has between about 0 and 30 branchesper 1000 carbon atoms, another component has between about 0 and 20branches per 1000 carbon atoms.

We have also recognized that by attaching a Group 8-10 polymerizationcatalyst to a solid support one can improve its functional groupcompatibility over that observed in the homogenous solutionpolymerization. In other words, the rate for the co-polymerization ofone or more olefin monomers of the type RCH═CHR⁸ with one or morefunctional olefin monomers of type CH₂═CH(CH₂)_(n)J is increased overthe homogeneous solution polymerization run under otherwise identicalconditions. In particular, we have found that by utilizing a supportedGroup 8-10 catalyst that monomers of the general formulaCH₂═CH(CH₂)_(n)J are copolymerized with other olefins (e.g. ethylene) atrates several orders of magnitude greater than that observed forcorresponding homogeneous systems. In this regard, examples of Group8-10 catalysts useful in this process include those described in U.S.Pat. Nos. 5,866,663; 5,886,224; 5,891,963; 5,880,323; 5,880,241 areincorporated herein by reference, along with WO 9623010, WO 9910391, WO9905189, WO 9856832, WO 9803559, WO 9847934, WO 9702298, WO 9830609, WO9842665, WO 9842664, WO 9847933, WO 9840420, WO 9840374.

Thus, in a further embodiment, there is provided a Group 8-10 transitionmetal catalyst having an improved rate for the co-polymerization of oneor more olefin monomers of the type RCH═CHR⁸ with one or more functionalolefin monomers of the formula CH₂═CH(CH₂)_(n)J, in an olefinpolymerization reaction which comprises combining said catalyst with asolid support, and optionally a Bronsted or Lewis acid in any order,prior to the utilization of said catalyst in said olefin polymerizationreaction.

R and R⁸ each, independently, represent a hydrogen, a hydrocarbyl, or afluoroalkyl, and may be linked to form a cyclic olefin;

n is an interger between 1-20;

J is a group selected from ester, acyl, acid halide, aldehyde, alkylamide, aryl, alkylamine, aryl amine, alkyl amido, aryl amido, alkylimido, aryl imido, ether, nitrile, alcohol, keto, amino, amido, imido,alkoxy thiol, thioalkoxy, acid, urea, sulfonamido, and sulfoester.Preferably, the compound of the formula CH₂═CH(CH₂)_(n)J is a compoundof the formula CH₂═CH(CH₂)_(n)CO₂R¹, wherein R¹ is hydrogen,hydrocarbyl, substituted hydrocarbyl, fluoroalkyl or silyl; and

n is an integer greater than 3;

In a further embodiment, the present invention provides an ethylenehomopolymer with a CDBl of less than 50%, preferably less than 40%, andmore preferably less than 30%.

In a further embodiment, the present invention provides a polyalkenewith a CDBl of less than 50%, which contains about 80 to about 150branches per 1000 methylene groups, and which contains for every 100branches that are methyl, about 30 to about 90 ethyl branches, about 4to about 20 propyl branches, about 15 to about 50 butyl branches, about3 to about 15 amyl branches, and about 30 to about 140 hexyl or longerbranches. Further preferred is a polyalkene of with a CDBl of less than40%, more preferably less than 30%. Further preferred are thosepolyalkenes which contain about 100 to about 130 branches per 1000methylene groups, and which contains for every 100 branches that aremethyl, about 50 to about 75 ethyl branches, about 5 to about 15 propylbranches, about 24 to about 40 butyl branches, about 5 to about 10 amylbranches, and about 65 to about 120 hexyl or longer branches.

In a further embodiment, there is provided a polyalkene with a CDBl ofless than 50% which contains about 20 to about 150 branches per 1000methylene groups, and which contains for every 100 branches that aremethyl, about 4 to about 20 ethyl branches, 1 to about 12 propylbranches, 1 to about 12 butyl branches, 1 to about 10 amyl branches, and0 to about 20 hexyl or longer branches. Further preferred are thepolyalkenes with a CDBl of less than 40%, more preferably less than 30%.Further preferred embodiments include the polyalkenes which containsabout 40 to about 100 branches per 1000 methylene groups, and whichcontains for every 100 branches that are methyl, about 6 to about 15ethyl branches, about 2 to about 10 propyl branches, about 2 to about 10butyl branches, about 2 to about 8 amyl branches, and about 2 to about15 hexyl or longer branches.

The polymers of the present invention include homopolymers of olefins,such as polyethylene, polypropylene, and the like, and olefincopolymers, including functional-group containing copolymers. As anexample, ethylene homopolymers can be prepared with strictly linear tohighly branched structures by variation of the catalyst structure,cocatalyst composition, and reaction conditions, including pressure andtemperature. The effect these parameters have on polymer structure isdescribed herein. These polymers and copolymers have a wide variety ofapplications, including use as packaging material and in adhesives.

In this disclosure certain chemical groups or compounds are described bycertain terms and symbols. These terms are defined as follows:

Symbols ordinarily used to denote elements in the Periodic Table taketheir ordinary meaning, unless otherwise specified. Thus, N, O, S, P,and Si stand for nitrogen, oxygen, sulfur, phosphorus, and silicon,respectively.

Examples of neutral Lewis acids include, but are not limited to,methylaluminoxane (hereinafter MAO) and other aluminum sesquioxides, R⁷₃Al, R⁷ ₂AlCl, R⁷AlCl₂ (where R⁷ is alkyl), organoboron compounds, boronhalides, B(C₆F₅)₃, BPh₃, and B(3,5-(CF₃)₂C₆H₃)₃. Examples of ioniccompounds comprising a cationic Lewis acid include: R⁹ ₃Sn[BF₄], (whereR⁹ is hydrocarbyl), MgCl₂, and H⁺X⁻, where X⁻ is a weakly coordinatinganion.

The term “weakly coordinating anion” is well-known in the art per se andgenerally refers to a large bulky anion capable of delocalization of thenegative charge of the anion. Suitable weakly coordinating anionsinclude, but are not limited to, PF₆ ⁻, BF₄ ⁻, SbF₆ ⁻, (Ph)₄B⁻ whereinPh=phenyl, ⁻BAr₄ wherein⁻BAr₄=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The coordinatingability of such anions is known and described in the literature(Strauss, S. et al., Chem. Rev. 1993, 93, 927).

Examples of neutral Lewis bases include, but are not limited to, (i)ethers, for example, diethyl ether or tetrahydrofuran, (ii) organicnitrites, for example acetonitrile, (iii) organic sulfides, for exampledimethylsulfide, or (iv) monoolefins, for example, ethylene, hexene orcyclopentene.

A “hydrocarbyl” group means a monovalent or divalent, linear, branchedor cyclic group which contains only carbon and hydrogen atoms. Examplesof monovalent hydrocarbyls include the following: C₁-C₂₀ alkyl; C₁-C₂₀alkyl substituted with one or more groups selected from C₁-C₂₀ alkyl,C₃-C₈ cycloalkyl or aryl; C₃-C₈ cycloalkyl; C₃-C₈ cycloalkyl substitutedwith one or more groups selected from C₁-C₂₀ alkyl, C₃-C₈ cycloalkyl oraryl; C₆-C₁₄ aryl; and C₆-C₁₄ aryl substituted with one or more groupsselected from C₁-C₂₀ alkyl, C₃-C₈ cycloalkyl or aryl; where the term“aryl” preferably denotes a phenyl, napthyl, or anthracenyl group.Examples of divalent (bridging) hydrocarbyls include: —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, and 1,2-phenylene.

A “silyl” group refers to a SiR₃ group wherein Si is silicon and R ishydrocarbyl or substituted hydrocarbyl or silyl, as in Si(SiR₃)₃.

A “heteroatom” refers to an atom other than carbon or hydrogen.Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur,selenium, arsenic, chlorine, bromine, silicon and fluorine.

A “substituted hydrocarbyl” refers to a monovalent or divalenthydrocarbyl substituted with one or more heteroatoms. Examples ofmonovalent substituted hydrocarbyls include:2,6-dimethyl-4-methoxyphenyl, 2,6-diisopropyl-4-methoxyphenyl,4-cyano-2,6-dimethylphenyl, 2,6-dimethyl-4-nitrophenyl,2,6-difluorophenyl, 2,6-dibromophenyl, 2,6-dichlorophenyl,4-methoxycarbonyl-2,6-dimethyiphenyl, 2-tert-butyl-6-chlorophenyl,2,6-dimethyl-4-phenylsulfonylphenyl,2,6-dimethyl-4-trifluoromethylphenyl,2,6-dimethyl-4-trimethylammoniumphenyl (associated with a weaklycoordinated anion), 2,6-dimethyl-4-hydroxyphenyl, 9-hydroxyanthr-10-yl,2-chloronapth-1-yl, 4-methoxyphenyl, 4-nitrophenyl, 9-nitroanthr-10-yl,—CH₂OCH₃, cyano, trifluoromethyl, or fluoroalkyl. Examples of divalent(bridging) substituted hydrocarbyls include: 4-methoxy-1,2-phenylene,1-methoxymethyl-1,2-ethanediyl, 1,2-bis(benzyloxymethyl)-1,2-ethanediyl,or 1-(4-methoxyphenyl)-1,2-ethanediyl.

A “sterically hindered aryl” means (i) a phenyl ring with hydrocarbyl,substituted hydrocarbyl, F, Cl, Br or silyl substituents at both the 2-and 6-positions, optionally substituted elsewhere with hydrocarbyl,substituted hydrocarbyl, F, Cl, Br, silyl, hydroxy, methoxy, nitro,cyano, phenylsulfonyl, CO₂Me, CO₂H, C(O)CH₃, CF₃, or fluoroalkylsubstituents, (ii) a 2-substituted napth-1-yl ring, optionallysubstituted elsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl,Br, silyl, hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO₂Me, CO₂H,C(O)CH₃, CF₃, or fluoroalkyl substituents, (iii) an 9-anthracenyl or1,2,3,4,5,6,7,8-octahydro-9-anthracenyl ring, optionally substitutedelsewhere with hydrocarbyl, substituted hydrocarbyl, F, Cl, Br, silyl,hydroxy, methoxy, nitro, cyano, phenylsulfonyl, CO₂Me, CO₂H, C(O)CH₃,CF₃, or fluoroalkyl substituents, or (iv) an aromatic substitutedhydrocarbyl with steric properties functionally equivalent (in thecontext of this invention) to one or more of the following stericallyhindered aryls: 2,6-dimethylphenyl, 2,4,6-trimethylphenyl,2,6-diisopropylphenyl, 2,6-dimethyl-4-nitrophenyl,2,6-dimethyl4-phenylsulfonylphenyl, 2-isopropyl-6-methylphenyl,2,6-bis(trifluoromethyl )phenyl, 2,6-dimethyl4-methoxyphenyl,2-methylnapth-1-yl, 9-anthracenyl,1,2,3,4,5,6,7,8-octahydro-9-anthracenyl, 2,6-diclorophenyl,2,6-dibromophenyl, 2-tert-butyl-6-methylphenyl,2-trimethylsilylnapth-1-yl, 2-chloro6-methylphenyl,4-cyano-2,6-dimethylphenyl, 2,6-diisopropyl-4-methoxyphenyl,2,4,6-tri-tert-butylphenyl, and 2-chloro4-tert-butylphenyl.

A “heteroatom connected mono-radical” refers to a mono-radical group inwhich a heteroatom serves as the point of attachment. Examples include:NH(2,6-dimethylphenyl) and SPh, where Ph is phenyl. Numerous otherexamples are given herein.

A “substituted silicon atom” refers to a —SiR⁹ ₂— group, wherein R⁹ is ahydrocarbyl or substituted hydrocarbyl.

A “substituted phosphorous atom” refers to a —P(O)(OR⁹)— group, whereinR⁹ is a hydrocarbyl or substituted hydrocarbyl.

A “substituted sulfur atom” refers to a —S(O)—, —SO₂—, or —S(NR⁹)₂—group, wherein R⁹ is a hydrocarbyl or substituted hydrocarbyl.

A “bridging group” refers to a divalent hydrocarbyl, divalentsubstituted hydrocarbyl, —C(O)—, —C(S)—, substituted silicon atom,substituted sulfur atom, substituted phosphorous atom, —CH₂C(O)—,—C(O)C(O)—, or 3,4,5,6-tetrafluoro-1,2-phenylene.

In certain cases, the bridging group, together with groups A and B, maycollectively form a divalent heteroatom substituted heterocycle;examples include:

A “mono-olefin” refers to a hydrocarbon containing one carbon-carbondouble bond.

A “suitable metal precursor” refers to a Group 8-10 transition metalcompound, preferably Ni, Co, Pd, and Fe compounds, which may be combinedwith compound X (preferably, compound III, VI, IX, XVII or XVIII,described below), and optionally a Lewis or Bronsted acid, to form anactive olefin polymerization catalyst. Examples include:(1,2-dimethoxyethane)nickel(II) dibromide, bis[(μ-chloro)(1, 2,3-η³-2-propenyl)nickel(II)], bis[(μ-chloro)(1, 2,3-η³-2-propenyl)palladium(II)], bis[(μ-chloro)(1, 2,3-η³-1-trimethylsilyloxy-2-propenyl)nickel(II)], CoBr₂, FeBr₂,bis(acetylacetonate)Ni(II), and [tetrakis(acetonitrile)Pd(II)][BF₄].

A “suitable nickel precursor” refers to a suitable metal precursorwherein the metal is nickel.

A “suitable nickel(O) precursor” refers to a suitable metal precursorwhich is a zerovalent nickel compound.

The term “fluoroalkyl” as used herein refers to a C₁-C₂₀ alkyl groupsubstituted by one or more fluorine atoms.

The term “polymer” as used herein is meant a species comprised ofmonomer units and having a degree of polymerization (DP) of ten orhigher.

The term “α-olefin” as used herein is a 1-alkene with from 3 to 40carbon atoms.

A “π-allyl” group refers to a monoanionic group with three sp² carbonatoms bound to a metal center in a η³-fashion. Any of the three sp²carbon atoms may be substituted with a hydrocarbyl, substitutedhydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connectedsubstituted hydrocarbyl, or O-silyl group. Examples of π-allyl groupsinclude:

The term π-benzyl group denotes an π-allyl group where two of the Sp²carbon atoms are part of an aromatic ring. Examples of π-benzyl groupsinclude:

A polymer with a “broad composition distribution” refers to a polymerthat comprises a plurality of compositions (preferably>5) having varyinglevels of branching. The polymers can be fractionated and the fractionshave levels of branching/1000 carbons that range from about 0 to about100 branches/1000 carbons.

“Composition Distribution Breadth Index” or CDBl is defined as theweight percent of the polymer molecules having a branching contentwithin 50% (that is, 25% on each side of the average total branching) ofthe average total branching of the bulk sample as determined by ¹H NMR.The CDBl is readily determined using well known fractionation techniquessuch as temperature rising elution fractionation (TREF). (See also WO97/48735 and WO 93/03093).

Sample Calculation

bulk polymer has 40 branches/1000 carbon atoms

30 - - - 40 - - - 50 (degree of branching within 50% of the averagebranching for bulk sample)

fractionate polymer using TREF or other technique

calculate the weight percent of the total polymer that has totalbranches as determined by NMR between 30 and 50. e.g. 5 grams of thetotal 10 grams charged when fractionated and analyzed has branchingbetween 30 and 50 branches/1000 carbon atoms. CDBl for this polymerwould be 50%.

A “free flowing polymer” refers to a non-tacky polymer that can betransported without significant agglomeration. In this context, thislack of significant agglomeration refers to polymer products which areuseful under commercial gas phase reactor conditions.

As used herein, the terms “monomer” and “olefin monomer” refer to theolefin or other monomer compound before it has been polymerized; theterm “monomer units” refers to the moieties of a polymer that correspondto the monomers after they have been polymerized.

In some cases, a compound Y is required as a cocatalyst. Suitablecompounds Y include a neutral Lewis acid capable of abstracting Q⁻ or W⁻to form a weakly coordinating anion, a cationic Lewis acid whosecounterion is a weakly coordinating anion, or a Bronsted acid whoseconjugate base is a weakly coordinating anion. Preferred compounds Yinclude: methylaluminoxane (hereinafter MAO) and other aluminumsesquioxides, R⁷ ₃Al, R⁷ ₂AlCl, R⁷AlCl₂ (wherein R⁷ is alkyl),organoboron compounds, boron halides, B(C₆F₅)₃, R⁹ ₃Sn[BF₄] (wherein R⁹hydrocarbyl), MgCl₂, and H⁺X⁻, wherein X⁻ is a weakly coordinatinganion. Examples of H⁺X⁻ are the ether solvate of hydrogentetrakis[3,5-bis(trifluoromethyl)phenyl]borate and montmorillinite clay.

Examples of “solid support” include inorganic oxide support materials,such as: talcs, silicas, titania, silica/chromia,silica/chromia/titania, silica/alumina, zirconia, aluminum phosphategels, silanized silica, silica hydrogels, silica xerogels, silicaaerogels, montmorillonite clay and silica co-gels as well as organicsolid supports such as polystyrene and functionalized polystyrene. (See,for example, Roscoe, S. B.; Frechet, J. M. J.; Walzer, J. F.; Dias, A.J.; “Polyolefin Spheres from Metallocenes Supported on Non-InteractingPolystyrene”, 1998, Science, 280, 270-273 (1998).) An especiallypreferred solid support is one which has been pre-treated with Ycompounds as described herein, most preferably with MAO. Thus, in apreferred embodiment, the catalysts of the present invention areattached to a solid support (by “attached to a solid support” is meantion paired with a component on the surface, adsorbed to the surface orcovalently attached to the surface) which has been pre-treated with acompound Y. Alternatively, the catalyst, the compound Y, and the solidsupport can be combined in any order, and any number of Y compounds canbe utilized; in addition, the supported catalyst thus formed, may betreated with additional quantities of compound(s) Y. In an especiallypreferred embodiment, the compounds of the present invention areattached to silica which has been pre-treated with MAO. Such supportedcatalysts are prepared by contacting the transition metal compound, in asubstantially inert solvent—by which is meant a solvent which is eitherunreactive under the conditions of catalyst preparation, or if reactive,acts to usefully modify the catalyst activity or selectivity—with MAOtreated silica for a sufficient period of time to generate the supportedcatalysts. Examples of substantially inert solvents include toluene,mineral spirits, hexane, CH₂Cl₂ and CHCl₃.

It is known to those skilled in the art that a variety of protocols maybe used to generate active polymerization catalysts comprisingtransition metal complexes of various nitrogen, phosphorous, oxygen andsulfur donor ligands. Examples of such protocols include (i) thereaction of a Group 8-10 metal dihalide complex of a bidentate N-donorligand with an alkylaluminum reagent, (ii) the reaction of a bidentateN-donor ligand with nickel(1,5-cyclooctadiene)₂ andHB(3,5-bis(trifluoromethyl)phenyl)₄, and (iii) the reaction of a Group8-10 metal dialkyl complex of a bidentate N-donor ligand with MAO orHB(3,5-bis(trifluoromethyl)phenyl)₄. In some cases, it is also possibleto react a bidentate N-donor ligand with nickel(1,5-cyclooctadiene)₂ andB(C₆F₅)₃ to obtain an active catalyst. Cationic (ligand)M(π-allyl)complexes with weakly coordinating counteranions, where M is a Group8-10 transition metal, are often suitable as catalyst precursors,requiring only exposure to olefin monomer and in some cases elevatedtemperatures (40-200° C.) or added Lewis acid, or both, to form anactive polymerization catalyst.

Isolable[(ligand)Ni(methyl)(O(CH₂CH₃)₂)][B(3,5-bis(trifluoromethyl)phenyl)₄] and[(ligand)Pd(methyl)(O(CH₂C H₃)₂)][B(3,5-bis(trifluoromethyl)phenyl)₄]salts may also serve as one component catalyst systems. More generally,a variety of (ligand)M(Q)(W) complexes, where “ligand” refers to acompound of formula X, M is a divalent Group 8-10 transition metal, andQ and W are univalent groups, or may be taken together to form adivalent group, may be reacted with one or more compounds, collectivelyreferred to as compound Y, which function as co-catalysts or activators,to generate an active catalyst of the form [(ligand)M(T)(L)]⁺X⁻, where Tis a hydrogen atom or hydrocarbyl, L is an olefin or neutral donor groupcapable of being displaced by an olefin, and X⁻ is a weakly coordinatinganion.

When Q and W are both halide, examples of suitable compounds Y include:methylaluminoxane (hereinafter “MAO”) and other aluminum sesquioxides,R⁰ ₃Al, R⁰ ₂AlCl, and R⁰AlCl₂ (wherein R⁰ is alkyl). When Q and W areboth alkyl, examples of suitable compounds Y include: MAO and otheraluminum sesquioxides, R⁰ ₃Al, R⁰ ₂AlCl, R⁰AlCl₂ (wherein R⁰ is alkyl),B(C₆F₅)₃, R¹⁶ ₃Sn[BF₄], H⁺X⁻, wherein X⁻ is a weakly coordinating anion,for example, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewisacidic or Bronsted acidic metal oxides, for example, montmorilloniteclay. In some cases, for example, when Q and W are both halide orcarboxylate, sequential treatment with a metal hydrocarbyl, followed byreaction with a Lewis acid or Bronsted acid, may be required to generatean active catalyst. Suitable examples of metal hydrocarbyls include:MAO, other aluminum sesquioxides, R⁰ ₃Al, R⁰ ₂AlCl, R⁰AlCl₂ (wherein R⁰is alkyl), Grignard reagents, organolithium reagents, and diorganozincreagents. Examples of suitable Lewis acids or Bronsted acids include:MAO, other aluminum sesquioxides, R⁰ ₃Al, R⁰ ₂AlCl, R⁰AlCl₂ (wherein R⁰is alkyl), B(C₆F₅)₃, R¹⁶ ₃Sn[BF₄], H⁺X⁻, wherein X⁻ is a weaklycoordinating anion, for example,tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and Lewis acidic orBronsted acidic metal oxides, for example, montmorillonite clay.

While not wishing to be bound by theory, the present inventors believethat the Lewis acid may be acting to further activate the catalystsprovided herein via coordination to one or more of those heteroatomswhich are not directly bound to the transition metal M, but which areπ-conjugated to the nitrogens which are bound to the transition metal M.Substituents which contain additional Lewis basic groups, including, butnot limited to, methoxy groups, positioned so as to further promote thebinding of the Lewis acid at such π-conjugated heteroatoms, are alsoincluded in this invention. A nonlimiting example of secondary Lewisacid binding would include the following:

wherein R¹, R², R⁵ ₁, and R⁶ are 2,6-dimethylphenyl; and X⁻ is a weaklycoordinating anion.

The polymerizations may be conducted as solution polymerizations, asnon-solvent slurry type polymerizations, as slurry polymerizations usingone or more of the olefins or other solvent as the polymerizationmedium, or in the gas phase. One of ordinary skill in the art, with thepresent disclosure, would understand that the catalyst could besupported using a suitable catalyst support and methods known in theart. Substantially inert solvents, such as toluene, hydrocarbons,methylene chloride and the like, may be used. Propylene and 1-butene areexcellent monomers for use in slurry-type copolymerizations and unusedmonomer can be flashed off and reused.

Temperature and olefin pressure have significant effects on polymerstructure, composition, and molecular weight. Suitable polymerizationtemperatures are preferably from about −100° C. to about 200° C., morepreferably in the 20° C. to 150° C. range.

After the reaction has proceeded for a time sufficient to produce thedesired polymers, the polymer can be recovered from the reaction mixtureby routine methods of isolation and/or purification.

In general, the polymers of the present invention are useful ascomponents of thermoset materials, as elastomers, as packagingmaterials, films, compatibilizing agents for polyesters and polyolefins,as a component of tackifying compositions, and as a component ofadhesive materials.

High molecular weight resins are readily processed using conventionalextrusion, injection molding, compression molding, and vacuum formingtechniques well known in the art. Useful articles made from them includefilms, fibers, bottles and other containers, sheeting, molded objectsand the like.

Low molecular weight resins are useful, for example, as synthetic waxesand they may be used in various wax coatings or in emulsion form. Theyare also particularly useful in blends with ethylene/vinyl acetate orethylene/methyl acrylate-type copolymers in paper coating or in adhesiveapplications.

Although not required, typical additives used in olefin or vinylpolymers may be used in the new homopolymers and copolymers of thisinvention. Typical additives include pigments, colorants, titaniumdioxide, carbon black, antioxidants, stabilizers, slip agents, flameretarding agents, and the like. These additives and their use in polymersystems are known per se in the art.

The molecular weight data presented in the following examples isdetermined at 135° C. in 1,2,4-trichlorobenzene using refractive indexdetection, calibrated using narrow molecular weight distributionpoly(styrene) standards.

EXAMPLES

Other features of the invention will become apparent in the course ofthe following descriptions of exemplary embodiments which are given forillustration of the invention and are not intended to be limitingthereof.

Example 1

Preparation of N,N′-bis(2,6-dimethylphyenl)oxalamide

2,6-dimethylaniline, triethylamine, and dichloromethane were dried bypassage through basic alumina. A 1 L round bottom flask, equipped with amagnetic stir bar and a 125 mL pressure-equalizing dropping funnelcapped by a nitrogen inlet adapter, was charged with 53.38 g of2,6-dimethylaniline, 250 mL of dichloromethane, and 44.76 g oftriethylamine. A solution of 25.34 g of oxalyl chloride in 80 mL ofdichloromethane was added dropwise under nitrogen with stirring andice-bath cooling over 1.2 hours to give a thick paste which had to beoccasionally swirled by hand to effect mixing. The mixture was allowedto stir at room temperature for 14 hours, then transferred to aseparatory funnel, washed 3 times with water, separated and concentratedunder reduced pressure (10 mm Hg) to give 63 g of crude solid. The crudeproduct was dissolved in a boiling mixture of 1.30 L of toluene and 2.85L of absolute ethanol, cooled to room temperature (about 23° C.) anddiluted with 260 mL of water, then allowed to crystallize for 16 hours.The resultant precipitate was isolated by vacuum filtration, washed withmethanol (3×100 mL) and dried to give 39.1 g (66%) as white crystals. Anadditional 9.5 g (16.1%) was recovered from the filtrate by furtherdilution with approximately 500 mL of water. Field desorption massspectrometry showed a parent ion peak at 296 m/z. ¹H NMR (300 MHz,CDCl₃, chemical shifts in ppm relative to TMS at 0 ppm): 2.29 (12 p, s),7.15 (6 p, m), 8.86 (2 p, br s).

Example 2

Preparation of N,N′-bis(2,6-diisopropylphyenl)oxalamide

2,6-Diisopropylaniline, triethylamine, and dichloromethane were dried bypassage through basic alumina. A 1 L round bottom flask, equipped with amagnetic stir bar and a 125 mL pressure-equalizing dropping funnelcapped by a nitrogen inlet adapter, was charged with 34.73 g of2,6-diisopropylaniline (previously distilled), 180 mL ofdichloromethane, and 18.30 g of triethylamine. A solution of 10.57 goxalyl chloride in 43 mL of dichloromethane was added dropwise undernitrogen with stirring and ice-bath cooling over 38 minutes to give athick paste which had to be occasionally swirled by hand to effectmixing. The mixture was allowed to stir at room temperature (about 23°C.) for 60 hours, then diluted with 700 mL of water to precipitate theproduct, which was isolated by filtration, washed with water andrecrystallized from boiling isopropanol (4 L) to afford 22.38 g (66%) ofwhite needles. Field desorption mass spectrometry showed a parent ionpeak at 408 m/z. ¹H NMR (500 MHz, CD₂Cl₂, chemical shifts in ppmrelative to TMS at 0 ppm): 1.22 (24 p, d, 6.8 Hz), 3.08 (4 p, septet,6.8 Hz), 7.25 (4 p, d, 7.5 Hz), 7.37 (2 p, t, 7.5 Hz), 8.86 (2 p, br s).

Example 3

Preparation of N,N′-bis (4-methoxy-2,6-dimethylphenyl)oxalamide

Triethylamine and dichloromethane were dried by passage through basicalumina. A 50 mL round bottom flask, equipped with a magnetic stir barand a small pressure-equalized dropping funnel capped by a nitrogeninlet adapter, was charged with 1.5 g of4-methoxy-2,6-dimethylphenylamine, 8 mL of dichloromethane, and 1.38 gof triethylamine. A solution of 0.39 of oxalyl chloride in 2 mL ofdichloromethane was added dropwise under a nitrogen atmosphere withstirring and ice-bath cooling over 35 min. The mixture was allowed tostir at room temperature for 14 hours, then transferred to a separatoryfunnel, washed with water, separated and concentrated under reducedpressure (10 mm Hg) to give 1.75 g solids. The crude product wasdissolved in 150 mL of boiling absolute ethanol and crystallized uponcooling to room temperature (about 23° C.). The resultant precipitatewas isolated by vacuum filtration, and dried to give 1.39 g (86%) aswhite crystals. Field desorption mass spectrometry showed a parent ionpeak at 356 m/z.

Example 4

Preparation of N¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride

A 1 L round bottom flask was charged with 30.0 g ofN,N′-bis(2,6-dimethylphenyl)oxalamide, 58.8 g of phosphorouspentachloride and 150 mL of dry toluene, and equipped with a magneticstir bar and a reflux condenser capped by a nitrogen inlet adapterconnected to a bubbler. The mixture was heated to reflux over 30minutes, then maintained at reflux under nitrogen for another 95 minutesto give a yellow solution. Heating was discontinued and the mixture wasallowed to cool to room temperature (about 23° C.). A short pathdistillation adapter and receiving flask was attached in place of thecondenser and the volatiles were removed under reduced pressure (1 mmHg), initially at room temperature, then at 100° C., to give 20.1 g(60%) of a granular yellow solid. Field desorption mass spectrometryshowed a parent ion peak at 332 m/z. ¹H NMR (300 MHz, C₆D₆, chemicalshifts in ppm relative to TMS at 0 ppm): 2.04 (12 p, s), 6.91 (6 p, s).

Example 5

Preparation of N¹,N²-bis(2,6-diisopropylphyenl)oxalodiimidoyl dichloride

A 500 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet adapter connected to abubbler was charged with 2.50 g ofN,N′-bis(2,6-diispropylphenyl)-oxalamide, 3.58 g of phosphorouspentachloride and 36 mL of dry toluene. The mixture was heated to refluxover 30 minutes, then maintained at reflux under nitrogen for another210 minutes to afford a clear yellow solution. Heating was discontinuedand the mixture was allowed to cool to room temperature (about 23° C.).A short path distillation adapter and receiving flask were attached inplace of the condenser and the volatiles were removed under reducedpressure (1 mm Hg), initially at room temperature, then at 100° C., togive a yellow oil, which slowly crystallized upon complete cooling. Theproduct was purified by column chromatography (SiO₂, Merck Grade 9385230-400 mesh, 60 Å; 3 v % ethyl acetate in hexane) to afford 1.49 g(55%) yellow crystals. Field desorption mass spectrometry showed aparent ion peak at 444 m/z.

Example 6

Preparation of N¹,N²-bis(4-methoxy-2,6-dimethylphyenl)oxalodiimidoyldichloride

A 50 mL round bottom flask was charged with 1.37 g ofN,N′-bis(4-methoxy-2,6-dimethylphenyl)oxalamide 1.88 g of phosphorouspentachloride and 15 mL of dry toluene, and equipped with a magneticstir bar and a reflux condenser capped by a nitrogen inlet adapterconnected to a bubbler. The mixture was heated, with stirring, at about100° C. until the evolution of HCl ceased. Then, another 0.22 g PCl₅ wasadded and the mixture was heated another 30 min at 80° C. After coolingto room temperature the mixture was transferred to a separatory funnel,and some crystallization occurred upon transfer. Complete transfer andre-dissolution of the product was accomplished by the addition ofdichloromethane. The organic layer was washed with saturated aqueoussodium bicarbonate, then concentrated in vacuo to afford 1.44 gcrystalline yellow solid. Field desorption mass spectrometry showed aparent ion peak at 392 m/z.

Example 7

Preparation of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet was charged with 504 mg ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 136 mg of sodiumhydride (60% mineral oil dispersion), 4.0 mL of dry tetrahydrofuran and0.140 mL of 1,2-ethanedithiol. The mixture was heated at reflux for 2hours, after which another 66 mg of sodium hydride dispersion was addedand the mixture was refluxed for an additional hour. After cooling, themixture was diluted with water and diethyl ether, and the ether layerwas separated, washed again with water, and dried with magnesium sulfateto afford a yellow-orange oil. Column chromatography (SiO₂, Merck Grade9385 230-400 mesh, 60 Å; 15 v % of ethyl acetate in hexane) afforded 296mg of a yellow oil which was crystallized by addition of hexane andcollected by vacuum filtration to give 219 mg of yellow granularcrystals. Field desorption mass spectrometry showed a parent ion peak at354 m/z. ¹H NMR (300 MHz, CDCl₃, chemical shifts in ppm relative to TMSat 0 ppm): 2.17 (12p, s), 3.27 (4p, br s), 6.4-7.12 (6 p, m).

Example 8

Preparation of 2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane

A 250 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by an argon inlet was sequentially charged with0.69 g of a 60% dispersion of sodium hydride in mineral oil, 3.34 g ofN¹,N²-bis(2,6-diisopropylphenyl)oxalodiimidoyl dichloride, 20 mL of drytetrahydrofuran, and 0.70 mL of 1,2-ethanedithiol. The mixture washeated under argon at reflux for 3 hours, after which another 0.25 g ofsodium hydride dispersion was added and the mixture was refluxed for anadditional 2.5 hours. After cooling, the mixture was diluted with waterand diethyl ether, and the ether layer was separated, washed with water,and dried with magnesium sulfate to afford a yellow-orange oil. Columnchromatography (SiO₂, Merck Grade 9385 230-400 mesh, 60 Å; 10 v % ethylacetate in hexane) afforded 3.14 g of a yellow-orange glass. Fielddesorption mass spectrometry showed a parent ion peak at 466 m/z. ¹H NMR(500 MHz, CD₂Cl₂, chemical shifts in ppm relative to TMS at 0 ppm):1.10-1.22 (12 p, m), 1.22-1.40 (12 p, m), 2.78-3.05 (4 p, m), 3.30 (4 p,br s), 7.05-7.25 (6 p, m).

Example 9

Preparation of 2,3-bis(phenylimino)-[1,4]dithiane

A 250 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by an argon inlet was sequentially charged with0.69 g of a 60% dispersion of sodium hydride in mineral oil, a freshlyprepared solution of 2.08 g N¹,N²-diphenyloxalodiimidoyl dichloride in20 mL of dry tetrahydrofuran, and 0.70 mL of 1,2-ethanedithiol. Themixture was heated under argon at reflux for 2 hours, after whichanother 0.30 g of sodium hydride dispersion was added and the mixturerefluxed for an additional 3 hours. After cooling, the mixture wasdiluted with water and diethyl ether, and the ether layer was separated,washed with water, and dried with magnesium sulfate to afford ayellow-orange gummy solid. Column chromatography (SiO₂, Merck Grade 9385230-400 mesh, 60 Å; 10 v % ethyl acetate in hexane) afforded 296 mg of ayellow oil which was crystallized by addition of hexane to give 0.161 gof yellow-orange granular crystals. Field desorption mass spectrometryshowed a parent ion peak at 298 m/z. ¹H NMR (300 MHz, CDCl₃, chemicalshifts in ppm relative to TMS at 0 ppm): 3.27 (4p, br s), 7.02 (4p,apparent d, 8.1 Hz), 7.19 (2p, apparent t, 7.2 Hz), 7.40 (4p, apparentt, 7.8 Hz).

Example 10

Preparation of2,3-bis(2,6-dimethylphenylimino)-2,3-dihydrobenzo[1,4]dithiine

A 100 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by an argon inlet was sequentially charged with0.294 g of a 60% dispersion of sodium hydride in mineral oil, 4 mL ofdry tetrahydrofuran, and 0.253 g of 1,2-benzenedithiol. After thebubbling had subsided, 0.600 g ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride was added. Themixture was stirred at 25° C. for 45 minutes, then heated to reflux over15 minutes and held at reflux for 1 hour. After cooling, the mixture wasdiluted with water and diethyl ether, and the ether layer was separated,washed with water, and dried with magnesium sulfate, and concentrated invacuo to give a yellow-orange oil. Column chromatography (SiO₂, MerckGrade 9385 230-400 mesh, 60 Å; 2 v % ethyl acetate in hexane) afforded0.412 g of a yellow-orange glass. Field desorption mass spectrometryshowed a parent ion peak at 402 m/z. ¹H NMR (300 MHz, CDCl₃, chemicalshifts in ppm relative to TMS at 0 ppm): 2.16 (12 p, s), 7.01-7.24 (10p, m).

Example 11

Preparation of 2,3-bis(4-methoxy-2.6-dimethylphenylimino)-[1,4]dithiane

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet was charged with 420 mg ofN¹,N²-bis(4-methoxy-2,6-dimethylphenyl)oxalodiimidoyl dichloride. To a50 mL pear flask was added 171 mg of sodium hydride (60% mineral oildispersion), 1.75 mL of dry tetrahydrofuran, and, cautiously, 0.11 mLethane dithiol. The resulting mixture was syringed into theN¹,N²-bis(4-methoxy-2,6-dimethylphenyl)oxalodiimidoyl dichloridesolution using 5 mL dry THF to complete the transfer. The reaction flaskwas heated at reflux for 3 hours, after which another 45 mg of sodiumhydride dispersion and another 20 μL ethane dithiol was added and themixture was refluxed for an additional hour. After cooling, the mixturewas diluted with water and diethyl ether, and the ether layerwas-separated, washed again with water, dried with magnesium sulfate,and concentrated to afford a yellow-orange solid. Column chromatography(SiO₂, Merck Grade 9385 230-400 mesh, 60 Å; 15 v % ethyl acetate inhexane) afforded 147 mg of a yellow powder. Field desorption massspectrometry showed a parent ion, peak at 414 m/z.

Example 12

Preparation of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet was charged with 504 mg ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 66 mg of sodiumhydride (60% mineral oil dispersion), 5.0 mL of dry tetrahydrofuran,0.230 mL of triethylamine (dried by passage through alumina) and 0.093mL of dry ethylene glycol. The mixture was heated at reflux for 105minutes, after which another 66 mg of sodium hydride dispersion wasadded and the mixture was refluxed for an additional hour. Aftercooling, the mixture was diluted with water and diethyl ether, and theether layer was separated, washed again with water, dried with magnesiumsulfate, and concentrated to afford a yellow oil. Crystallization fromheptane gave rosettes of off-white crystals (225 mg, 1 st crop). Fielddesorption mass spectrometry showed a parent ion peak at 322 m/z. ¹H NMR(300 MHz, CDCl₃, chemical shifts in ppm relative to TMS at 0 ppm): 2.20(12 p, s), 4.35 (4 p, s), 6.94 (2 p, m), 7.05 (4 p, m).

Example 13

Preparation, of5-methoxymethyl-2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by an argon inlet was charged with 504 mg ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 155 mg of sodiumhydride (60% mineral oil dispersion), 3.5 mL of dry tetrahydrofuran and188 mg of 3-methoxy-1,2-propanediol. The mixture was heated to refluxover 10 min and held at reflux for 2 hours. After cooling, the mixturewas diluted with diethyl ether, and washed with water (2×100 mL), anddried with magnesium sulfate and concentrated in vacuo to afford 329 mgof a yellow oil. Column chromatography (SiO₂, Merck Grade 9385 230-400mesh, 60 Å; 20 v % of ethyl acetate in hexane) afforded 216 mg of aglassy yellow solid. Field desorption mass spectrometry showed a parention peak at 366 m/z. ¹H NMR (300 MHz, CDCl₃, chemical shifts in ppmrelative to TMS at 0 ppm): 2.18 (12 p, s), 3.31 (3 p, s), 3.45-3.65 (2p, m), 4.20-4.40 (2 p, m), 4.40-4.55 (1 p, m), 6.80-7.15 (6 p, m).

Example 14

Preparation of2,3-bis(benzyloxymethyl)-5,6-bis(2,6-dimethylphenylimino)-[1,4]dioxane

A 100 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by an argon inlet was charged with 265 mg ofsodium hydride (60% mineral oil dispersion), 7.5 mL of drytetrahydrofuran, 1.0 g of 3-methoxy-1,2-propanediol and 1.0 g ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride. The yellowmixture was heated to reflux over 15 min and became very viscous. Moretetrahydrofuran (5 mL) was added and the mixture was stirred with aglass rod, then heated for another 30 min. Next, an additional 220 mg ofsodium hydride (60% mineral oil dispersion) and an additional 10 mLtetrahydrofuran were added. Most of the yellow color was discharged withthe second addition of sodium hydride, rendering the very viscousreaction mixture light brown. Heating was continued for about 15 minmore, and after cooling, the mixture was diluted with diethyl ether andwashed with water to remove the sodium chloride. Column chromatography(SiO₂, Merck Grade 9385 230-400 mesh, 60 Å; 2 v % of ethyl acetate inhexane) afforded a beige gummy solid. Field desorption mass spectrometryshowed a parent ion peak at 562 m/z. ¹H NMR (300 MHz, CDCl₃, chemicalshifts in ppm relative to TMS at 0 ppm): 2.17 (12 p, s), 3.63 (4 p, brs), 4.38 (2 p, d, 12.6 Hz), 4.47 (2 p, d, 12.6 Hz), 4.56 (2 p, br s),6.85-7.4 (16 p, m).

Example 15

Preparation of 2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet was charged with 1.0 g ofN¹,N²-bis(2,6-diisopropylphenyl)oxalodiimidoyl dichloride, 268 mg ofsodium hydride (60% mineral oil dispersion), 4.0 mL of drytetrahydrofuran, and 212 mg of dry ethylene glycol. Under an argonatmosphere, the mixture was heated to 65° C. held at that temperaturefor 90 minutes. The mixture was then quickly heated to reflux and heldat reflux for 30 minutes more. After cooling, the mixture was dilutedwith 50 mL diethyl ether, and washed with water, dried with magnesiumsulfate, and concentrated in vacuo to afford a light straw-yellow oil(903 mg). Column chromatography (SiO₂, Merck Grade 9385 230-400 mesh, 60Å; 8 v % ethyl acetate in hexane) afforded 257 mg of a pale green glass.Field desorption mass spectrometry showed a parent ion peak at 434 m/z.¹H NMR (300 MHz, CDCl₃, chemical shifts in ppm relative to TMS at 0ppm): 1.24 (24 p, d, 6.6 Hz), 3.00 (4p, septet, 6.6 Hz), 4.31 (4 p, brs), 7.04-7.20 (6 p, m).

Example 16

Preparation of 2,3-bis(2,6-dimethylphenylimino)-4-methylmorpholine

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet adapter was charged with 503mg of N¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 346 mgtriethylamine, 4 mL dry, deoxygenated toluene, and 0.135 mL2-(methylamino)ethanol. The mixture was heated to reflux under nitrogenover 30 minutes and maintained at reflux for another 4.25 hours. Aftercooling, the mixture was diluted with 45 mL diethyl ether and washedthree times with water (110 mL total). The ether extract was dried withmagnesium sulfate, filtered and concentrated under reduced pressure (10mm Hg) to give a light-colored solid (512 mg). Recrystallization fromheptane/dichloromethane gave 138 mg pale off-white crystals (firstcrop). Field desorption mass spectrometry showed a parent ion peak at335 m/z. ¹H NMR (300 MHz, CDCl₃, chemical shifts in ppm relative to TMSat 0 ppm): 1.73 (6 p, s), 2.10 (6 p, s), 3.27 (3 p, s), 3.55-3.65 (2 p,m), 4.16-4.26 (2 p, m), 6.65-6.95 (6 p, m).

Example 17

Preparation of 2.3-bis(2.6-diisopropylphenylimino)-4-methylmorpholine

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet adapter was charged with 725mg of N¹,N²-bis(2,6-diisopropylphenyl)oxalodiimidoyl dichloride, 143 mgof sodium hydride (60% mineral oil dispersion), 4 mL drytetrahydrofuran, and 0.144 mL 2-(methylamino)ethanol. The mixture wasstirred at room temperature for 4 hours, and allowed to stand at roomtemperature for another 5 days. The mixture was diluted with diethylether and washed water. The ether extract was concentrated under reducedpressure (10 mm Hg) to give a yellow oil which partially crystallizedover several hours). Column chromatography (SiO₂, Merck Grade 9385230-400 mesh, 60 Å; 12 v % of ethyl acetate in hexane) afforded 156 mglight yellow crystalls. Field desorption mass spectrometry showed aparent ion peak at 447 m/z. ¹H NMR (300 MHz, CDCl₃, chemical shifts inppm relative to TMS at 0 ppm): 0.86 (6 p, d, 7.2 Hz), 1.04 (6 p, d, 7.2Hz), 1.15 (6 p, d, 7.2 Hz), 1.18 (6 p, d, 7.2 Hz), 2.27 (2 p, apparentseptet, 7.2 Hz), 2.97 (2 p, apparent septet, 7.2 Hz), 3.28 (3 p, br s),3.55-3.65 (2 p, m), 4.14-4.22 (2 p, m), 6.80-7.02 (6 p, m).

Example 18

Preparation of 1,3-bis-(2,6-dimethyl-phyenl)-4,5-bis-(2,6-dimethyl-phenylimino)-imidazolidin-2-one

In a 250 mL round bottom flask, 1.0 g ofN¹,N²,N³,N⁴-tetrakis(2,6-dimethylphenyl)oxalamidine was dissolved in 35mL dry, deoxygenated dichloromethane while stirring under an argonatmosphere. 0.67 mL dry triethylamine was added, followed by 240 mgtriphosgene. With the addition of the triphosgene, the color shiftedfrom pale yellow to chrome yellow. The mixture was allowed to stir for16 h at room temperature, after which time an additional 460 mg oftriphosgene was added. After about 15 min, 10 mg dimethylamino pyridineand an additional 240 mg triphosgene were added. After about 15 minmore, another 220 mg triphosgene and about 0.5 g dimethylamino pyridinewere added. The mixture was washed with saturated aqueous sodiumbicarbonate, then with water, and then concentrated in vacuo to afford ayellow powder. Column chromatography (SiO₂, Merck Grade 9385 230-400mesh, 60 Å; 4 v % ethyl acetate in hexane) afforded 763 mg of a chromeyellow powder. Field desorption mass spectrometry showed a parent ionpeak at 528 m/z. ¹H NMR (300 MHz, CDCl₃, chemical shifts in ppm relativeto TMS at 0 ppm): 2.01 (12 p, s), 2.32 (12 p, s), 6.4-7.3 (12 p, m).

Example 19

Preparation of1,3-bis(4-methoxy-2,6-dimethylphyenl)-4,5-bis-(4-methoxy-2.6-dimethylphenylimino)imidazolidin-2-one

A 100 mL round bottom was equipped with a magnetic stirrer and chargedwith 0.75 mL dry triethylamine, 6 mL dry and deoxygenateddichloromethane, and 0.335 9N¹,N²,N³,N⁴-tetrakis(4-methoxy-2,6-dimethylphenyl)oxalamidine. Withstirring, 178 mg triphosgene was added, and the flask was quickly cappedwith a septum. A precipitate formed and the color shifted from yellow toorange. After 2.5 days another 78 mg triphosgene was added, and thereaction left to stir another 2 hours. 150 mg more triphosgene wasadded, and the reaction left to stir for another 16 hrs. The reactionmixture was diluted with 50 mL diethyl ether and washed with water (2×50mL). The aqueous washings were back-extracted with dichloromethane. Theorganic layers were combined and dried over magnesium sulfate, andconcentrated in vacuo to afford an orange oil. Upon addition of diethylether to the oil, small orange crystals formed. The compound wasisolated on a vacuum filter and washed with diethyl ether to afford 216mg yellow-orange microcrystalline powder. Field desorption massspectrometry showed a parent ion peak at 648 m/z. ¹H NMR (500 MHz,CD₂Cl₂, chemical shifts in ppm relative to TMS at 0 ppm): 1.98 (12 p,broad hump), 2.25 (12 p, broad hump), 3.63 (6 p, broad hump), 3.75 (6 p,broad hump), 6.32 (4 p, broad hump), 6.59 (4 p, broad hump).

Example 20

Preparation of N¹,N²,N³,N⁴-tetrakis(2,6-dimethylphyenl)oxalamidine

A 1 L round bottom flask equipped with a magnetic stir bar and a refluxcondenser capped by a nitrogen inlet was charged with 5.6 g ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 43 mL of drytoluene and 32.7 g of 2,6-dimethylaniline (dried by passage throughalumina). The mixture was heated to reflux under nitrogen over 30minutes, then maintained at reflux another 3 hours. After cooling, themixture was diluted with 206 g of absolute ethanol and 45 g of water toproduce copious amounts of precipitate. Isolation by vacuum filtration,with ethanol (600 mL) and heptane (600 mL) washes, and subsequentdrying, gave 6.1 g (72%) as pale yellow crystals. Field desorption massspectrometry showed a parent ion peak at 502 m/z. ¹H NMR (300 MHz,CDCl₃, chemical shifts in ppm relative to TMS at 0 ppm): 2.16 (24 p, s),6.75 (12 p, s), 8.6 (2 p, br s).

Example 21

Preparation ofN¹,N²,N³,N⁴-tetrakis(4-methoxy-2,6-dimethylphyenl)oxalamidine

A 500 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet was charged with 1.0 g ofN¹,N²-bis(4-methoxy-2,6-dimethylphenyl)oxalodiimidoyl dichloride, 24 mLof dry toluene and 854 mg of 4-methoxy-2,6-dimethylphenylamine, and 0.90mL triethylamine (dried by passage through alumina). The mixture washeated to reflux under nitrogen over 30 minutes, then maintained atreflux another 14 hours. After cooling, the mixture was diluted withdichloromethane and washed with water. The impure compound was adsorbedonto SiO₂, and column chromatography (SiO₂, Merck Grade 9385 230-400mesh, 60 Å; 12.5 v % ethyl acetate in hexane) afforded 340 mg of ayellow powder. Field desorption mass spectrometry showed a parent ionpeak at 622 m/z.

Example 22

Preparation of 1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)Piperazine

A 25 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet adapter was charged with0.50 g of N¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 1.1 mLof N,N′-dimethylethylenediamine and 4.0 mL of dry toluene. The mixturewas heated to reflux under nitrogen over 15 minutes and maintained atreflux for another 30 minutes. After cooling, the mixture was dilutedwith diethyl ether and washed three times with water. The ether extractwas dried with magnesium sulfate, filtered and concentrated underreduced pressure (10 mm Hg) to give a yellow solid (0.50 g).Recrystallization from heptane gave pale yellow crystals. Fielddesorption mass spectrometry showed a parent ion peak at 348 m/z. ¹H NMR(300 MHz, CDCl₃, chemical shifts in ppm relative to TMS at 0 ppm): 1.83(br s, 12 p), 2-3.4 (two very broad humps, 4 p), 3.42 (br s, 6 p), 6.66(t, 2p), 6.84 (d, 4p).

Example 23

Preparation of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 100 mg of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 79 mg of(1,2-dimethoxyethane)nickel(II) dibromide under an inert atmosphere.Dry, deoxygenated dichloromethane (5 mL) was added and the mixture wasstirred under an argon atmosphere, turning red-brown within about 5minutes and slowly producing a red-brown crystalline precipitate. After1 hour, another 5 mL of dichloromethane was added. The mixture wasstirred another 21 hours at 21° C., then diluted with 10 mL of dry,deoxygenated hexane and stirred another 8 hours. The supernatant wasremoved via a filter paper-tipped cannula, and the residue dried invacuo at 1 mm Hg to afford 116 mg of red-brown crystals.

Example 24

Preparation of the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane

A Schlenk flask equipped with a magnetic stir bar was charged with 79 mgof 2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane (0.17 mmol) and 49mg of (1,2-dimethoxyethane)nickel(II) dibromide (0.16 mmol)under anargon atmosphere. Dry, deoxygenated dichloromethane (15 mL) was addedand the mixture was stirred under an argon atmosphere, turning red-brownwithin about 10 minutes. After 2 hours, the CH₂Cl₂ was removed in vacuo.The resulting red-brown solid was washed with 2×10 mL of hexane and thesolid was dried in vacuo for several hours affording 76 mg of a brownsolid.

Example 25

Preparation of the nickel dibromide complex of2,3-bis(phenylimino)-[1,4]dithiane

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 151 mg of 2,3-bis(phenylimino)-[1,4]dithianeand 123 mg of (1,2-dimethoxyethane)nickel(II) dibromide under an inertatmosphere. Dry, deoxygenated dichloromethane (10 mL) was added and themixture was stirred under an argon atmosphere, turning dark brown withinabout 5 minutes and slowly producing a red-brown crystallineprecipitate. After 80 minutes, the mixture was concentrated to apparentdryness under a stream of argon, then further dried in vacuo for 1 hourat 50 mTorr to afford a red-brown powder.

Example 26

Preparation of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-2, 3-dihydrobenzo[1,4]dithiine

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 110 mg of2,3-bis-(2,6-dimethylphenylimino)-2,3-dihydrobenzo[1,4]dithiine and 71mg of (1,2-dimethoxyethane)nickel(II) dibromide under an inertatmosphere. Dry, deoxygenated dichloromethane (8 mL) was added and themixture was stirred under an argon atmosphere, quickly turningred-brown. The mixture was stirred for 1 hour, concentrated to drynessunder a stream of argon, then further dried in vacuo for 1 hour at 50mTorr to yield a red-brown crystalline powder.

Example 27

Preparation of the nickel dibromide complex of2,3-bis(4-methoxy-2,6-dimethylphenylimino)-[1,4]dithiane

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 147 mg of2,3-bis(4-methoxy-2,6-dimethylphenylimino)-[1,4]dithiane and 93 mg of(1,2-dimethoxyethane)nickel(II) dibromide under an inert atmosphere.Dry, deoxygenated dichloromethane (10 mL) was added and the mixture wasstirred under an argon atmosphere, turning dark brown almostimmediately, and producing a brown precipitate. After 2 hours, 10 mL dryand deoxygenated hexane was added to complete the precipitation. Thesupernatant was removed via filter paper-tipped cannula, the residuedried in vacuo (0.5 mm Hg) for 14 h to obtain the product as a brownmicrocrystalline solid.

Example 28

Preparation of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 100 mg of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane and 87 mg of(1,2-dimethoxyethane)nickel(II) dibromide under an inert atmosphere.Dry, deoxygenated dichloromethane (5 mL) was added and the mixture wasstirred under an argon atmosphere, slowly producing a brown crystallineprecipitate. After 1 hour, another 5 mL of dichloromethane was added.The mixture was stirred another 21 hours at 21° C., then diluted with 10mL of dry, deoxygenated hexane and stirred another 8 hours. Thesupernatant was removed via a filter paper-tipped cannula, and theresidue dried in vacuo at 1 mm Hg to afford 117 mg of brown crystals.

Example 29

Preparation of the nickel dibromide complex of2,3-bis(benzyloxymethyl)-5,6-bis(2,6-dimethylphenylimino)-[1,4]dioxane

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 172 mg of2,3-bis(benzyloxymethyl)-5,6-bis(2,6-dimethylphenylimino)-[1,4]dioxaneand 85 mg of (1,2-dimethoxyethane)nickel(II) dibromide under an inertatmosphere. Dry, deoxygenated dichloromethane (12 mL) was added and themixture was stirred under an argon atmosphere, almost immediatelyturning red-brown. After 1.75 hours, the mixture was concentrateddryness under a stream of argon for 16 h, then further dried in vacuo toafford 182 mg of a red-brown crystalline powder.,

Example 30

Preparation of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-4-methylmorpholine.

A 25 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 100 mg of2,3-bis(2,6-dimethylphenylimino)-4-methylmorpholine and 84 mg of(1,2-dimethoxyethane)nickel(II) dibromide under an inert atmosphere.Dry, deoxygenated dichloromethane (5 mL) was added and the mixture wasstirred under an argon atmosphere for 1 hour, after which another 5 mLdichloromethane was added. After 16 hours, the mixture was diluted with10 mL hexane, and the supernatent was removed via a filter paper tippedcannula, and the residue was dried in vacuo to obtain 139 mg greencrystals.

Example 31 Reaction of 1,3-bis-(2,6-dimethyl-phenyl)-45-bis-(2,6-dimethyl-phenylimino)-imidazolidin-2-one,(1,2-dimethoxyethane)nickel(II) dibromide, and silver tetrafluoroborate

In an argon filled glove box, a flame-dried Schlenk flask equipped witha magnetic stir bar was charged with 159.6 mg of1,3-bis-(2,6-dimethyl-phenyl)4,5-bis-(2,6-dimethyl-phenylimino)-imidazolidin-2-oneand 92.7 mg of (1,2-dimethoxyethane)nickel(II) dibromide and 59.4 mgsilver tetrafluoroborate. The flask was wrapped in aluminum foil, and onthe Schlenk line, under an argon atmosphere, 10 mL dry tetrahydrofuranwas added. A white precipitate immediately separated. The mixture wasstirred for 25 min, then the supernatant was transferred via filterpaper-tipped cannula to a dry septum-capped vial. The supernatant wasconcentrated to dryness under a stream of dry argon for 16 h to afford256 mg of a yellow crystalline powder.

Example 32

Preparation of the nickel dibromide complex of1,3-bis(4-methoxy-2,6-dimethylphenyl)-4,5-bis(4-methoxy-2,6-dimethylphenylimino)imidzolidin-2-one

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 101 mg of1,3-bis(4-methoxy-2,6-dimethylphenyl)-4,5-bis(4-methoxy-2,6-dimethylphenylimino)imidazolidin-2-oneand 40 mg of (1,2-dimethoxyethane)nickel(II) dibromide under an inertatmosphere. Dry, deoxygenated dichloromethane (10 mL) was added and themixture was stirred under an nitrogen atmosphere, slowly turning darkred-brown over 3 hours. After 2 more hours, the supernatant was removedto a flame-dried Schlenk flask via a filter paper-tipped cannula,diluted with 10 mL dry, deoxygenated hexane, and concentrated to drynessunder a stream of nitrogen to give a mixture of a tan microcrystallinepowder and large, well-defined dark brown crystals. The latter wereseparated and used without further purification.

Example 33

Preparation of the nickel dibromide complex of1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 48 mg of1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine and 35 mg of(1,2-dimethoxyethane)nickel(II) dibromide under an inert atmosphere.Dry, deoxygenated dichloromethane (5 mL) was added and the mixture wasstirred under an argon atmosphere, turning green within about 5 minutesand slowly producing a green precipitate. After a total of 7 hours, thevolatiles were removed under reduced pressure (1 mm Hg) and the residuewas washed with 2×5 mL of dry, deoxygenated diethyl ether. The resultantgreen solid was dried under reduced pressure (1 mm Hg).

Example 34 Synthesis of

In the glove box, a Schlenk flask was charged with 500 mg of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and 250 mg(1,5-cyclooctadiene)palladium methyl chloride. The flask was removedform the box and placed under an argon atmosphere. To the solid mixturewas added 20 ml of methylene chloride resulting in an orange solution.The mixture was left to stir for 4 hours. After 4 hours, 20 ml of hexanewas added resulting in the precipitation of an orange solid. The solventwas removed via filter cannula leaving a red/orange solid. The solid wassubsequently washed 3×10 ml of hexane and dried in vacuo resulting in490 mg of the complex (83 yield). ¹H NMR is consistent with the proposedstructure.

Example 35 Synthesis of

In the glove box, a Schlenk flask was charged with 490 mg of2,3-bis(2,6-diisopropylphenylimino)[1,4]dithiane palladium methylchloride and 738 mg of NaBAr₄ where Ar -3,5-bis-trifluromethylphenyl.The flask was removed form the box and placed under an argon atmosphere.To the solid mixture was added 25 ml of methylene chloride and 0.2 ml ofacetonitrile resulting in an orange solution. The mixture was left tostir for 3 hours. After 3 hours, the solution was transfered via filtercannula leaving a gray solid (NaCl). The solvent was subsequentlyremoved in vacuo resulting in a orange glass (1.1 g of the complex, 90%yield). ¹H NMR is consistent with the proposed structure.

Example 36

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 5.3 mg of the nickel dibromidecomplex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The flask wasevacuated and refilled with ethylene, then charged with 75 mL of dry,deoxygenated toluene. The resultant suspension was cooled to 0° C. andallowed to equilibrate with 1 atmosphere ethylene for 15 minutes, thentreated with 4.0 mL of a 10 wt % solution of MAO in toluene and stirredunder 1 atmosphere ethylene. A white polyethylene precipitate (with afaint red-brown tinge) was observed within minutes. After 10 minutes,the mixture was quenched by the addition of acetone (50 mL), methanol(50 mL) and 6 N aqueous HCl (100 mL). The swollen polyethylene whichseparated was isolated by vacuum filtration and washed with water,methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg)for 48 hours to give 2.5 g of a white polyethylene. A similar reactionat 21.5° C. using 0.104 mg of the nickel complex (100 μL of a 1.04 mg/mLstock solution in o-difluorobenzene) gave 426 mg polyethylene after 14minutes reaction (359,000 Turnovers per hour (TO/h)). ¹H NMR: 24branches/1000 carbon atoms. GPC: M_(n)=810,000; M_(w)/M_(n)=2.3.

Example 37

Polymerization of ethylene using a catalyst generated in situ from2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane,bis(1,5-cyclooctadiene)nickel(O) and HB(Ar)₄(Ar=3,5-bis(trifluoromethyl)phenyl)

A 250 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 20 mg ofbis(1,5-cyclooctadiene)nickel(O), 33 mg of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane, and 83 mg of the ethersolvate HB(Ar)₄. The flask was evacuated and refilled with ethylene,then charged with 75 mL of dry, deoxygenated toluene. The deep violetsolution which resulted was stirred under ethylene at 25° C. for 30minutes, then quenched by addition of acetone (50 mL), and methanol (50mL). The polyethylene which separated was isolated by vacuum filtrationand washed with acetone, then dried under reduced pressure (0.5 mm Hg)for 18 hours to give 339 mg of white polyethylene (332 TO/h). ¹H NMR: 47branches/1000 carbon atoms. GPC: M_(n)=180,000; M_(w)/M_(n)=2.4.

Example 38

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar wascharged with 0.5 mL of a stock solution (10 mg in 10 mL CH₂Cl₂) of thenickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The flask was evacuatedand refilled with ethylene, and charged with 75 mL of dry, deoxygenatedtoluene. The reaction flask was placed in a water bath (23° C.) andtreated with 1.0 mL of a 10 wt % solution of MAO in toluene and stirredunder 1 atmosphere ethylene. A white polyethylene precipitate wasobserved within seconds. After 5 minutes, the mixture was quenched bythe addition of acetone, methanol and 6 N aqueous HCl. The swollenpolyethylene which separated was isolated by vacuum filtration andwashed with acetone. The resulting polymer was dried for several hoursin a vacuum oven at 80° C. 580 mg of a white rubbery solid was isolated(285,000 TO/h). DSC: (2nd heat) broad melt with an endothermic maximumat 87° C. ¹H NMR, 37 branches/1000 carbon atoms. GPC: M_(n)=186,000;M_(w)/M_(n)=2.06.

Example 39

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar wascharged with 0.5 mL of a stock solution (10 mg in 10 mL CH₂Cl₂) of thenickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane. The flask wasevacuated and refilled with ethylene, and charged with 75 mL of dry,deoxygenated toluene. The reaction flask was placed in a water bath andtreated with 1.0 mL of a 10 wt % solution of MAO in toluene and stirredunder 1 atmosphere ethylene. After 10 minutes, the mixture was quenchedby the addition of acetone, methanol and 6 N aqueous HCl. The swollenpolyethylene which separated was isolated by vacuum filtration andwashed with acetone. The resulting polymer was dried for several hoursin a vacuum oven at 80° C. 210 mg of a white rubbery amorphous polymerwas isolated (63,000 TO/h). DSC: (2nd heat) broad melt with anendothermic maximum at 6° C. ¹H NMR: 92 branches/1000 carbon atoms. GPC:M_(n)=146,000; M_(w)/M_(n)=1.85.

Example 40

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)[1,4]dithiane in the presence of MAO(modified methylaluminoxane; 23% iso-butylaluminoxane)

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure that the reactor was dry. The reactor was cooled andpurged with argon. Under an argon atmosphere, the autoclave was chargedwith 150 mL of toluene and 0.3 mL of a stock solution (10 mg in 10 mLCH₂Cl₂) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was heatedto 40° C. and 2 mL of MMAO in heptane (6.42 wt % aluminum) was added.The reactor was rapidly pressurized to 100 psig with ethylene and thetemperature ramped up to 50° C. After 10 minutes at 50° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated and dried for several hours ina vacuum oven at 80° C. 4.8 g of a white rubbery solid was isolated(2,000,000 TO/h). DSC: (2nd heat) broad melt with an endothermic maximumat 97° C. ¹H NMR: 28 branches/1000 carbon atoms. GPC: M_(n)=155,000;M_(w)/M_(n)=2.10.

Example 41

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of MMAO(23% iso-butylaluminoxane)

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure that the reactor was dry. The reactor was cooled andpurged with argon. Under an argon atmosphere, the autoclave was chargedwith 150 mL of toluene and 0.3 mL of a stock solution (10 mg in 10 mLCH₂Cl₂) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was cooledto 150 C and 2 mL of MMAO in heptane (6.42 wt % aluminum) was added. Thereactor was rapidly pressurized to 100 psig with-ethylene and thetemperature ramped up to 25° C. After 10 minutes at 25° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated and dried for several hours ina vacuum oven at 80° C. 4.4 g of a white rubbery polyethylene wasisolated (1,800,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 125° C. ¹H NMR: 6 branches/1000 carbon atoms. GPC:M_(n)=598,000; M_(w)/M_(n)=2.12.

Example 42

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of MMAO(23% iso-butylaluminoxane)

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure that the reactor was dry. The reactor was cooled andpurged with argon. Under an argon atmosphere, the autoclave was chargedwith 150 mL of toluene and 1.0 mL of a stock solution (10 mg in 10 mLCH₂Cl₂) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was heatedto 55° C. and 2 mL of MMAO in heptane (6.42 wt % aluminum) was added.The reactor was rapidly pressurized to 100 psig with ethylene and thetemperature ramped up to 65° C. After 10 minutes at 65° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated and dried for several hours ina vacuum oven at 80° C. 5.3 g of a white rubbery solid was isolated(640,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at 78°C. ¹H NMR: 47 branches/1000 carbon atoms. GPC: M_(n)=86,000;M_(w)/M_(n)=1.95.

Example 43

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-1,4]dithiane in the presence of MMAO(23% iso-butylaluminoxane)

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure that the reactor was dry. The reactor was cooled andpurged with argon. Under an argon atmosphere, the autoclave was chargedwith 150 mL of toluene and 1.0 mL of a stock solution (10 mg in 10 mLCH₂Cl₂) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The autoclave was heatedto 70° C. and 2 mL of MMAO in heptane (6.42 wt % aluminum) was added.The reactor was rapidly pressurized to 100 psig with ethylene and thetemperature ramped up to 80° C. After 10 minutes at 80° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated and dried for several hours ina vacuum oven at 80° C. 3.5 g of a white rubbery solid was isolated(440,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at 67°C. ¹H NMR: 53 branches/1000 carbon atoms. GPC: M_(n)=87,000;M_(w)/M_(n)=1.66.

Example 44

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence ofMMAO (23% iso-butylaluminoxane)

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure that the reactor was dry. The reactor was cooled andpurged with argon. Under an argon atmosphere, the autoclave was chargedwith 150 mL of toluene and 0.5 mL of a stock solution (10 mg in 10 mLCH2Cl2) of the nickel dibromide complex of2,3-bis(2,6-di-iso-propylphenylimino)-[1,4]dithiane. The autoclave washeated to 40° C. and 2 mL of MMAO in heptane (6.42 wt % aluminum) wasadded. The reactor was rapidly pressurized to 100 psig with ethylene andthe temperature ramped up to 50° C. After 10 minutes at 50° C., thereaction was quenched by the addition of acetone, and methanol. Theswollen polyethylene which separated was isolated and dried for severalhours in a vacuum oven at 80° C. 2.4 g of a white rubbery solid wasisolated (700,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 46° C. ¹H NMR: 75 branches/1000 carbon atoms. GPC:M_(n)=966,000; M_(w)/M_(n)=1.70.

Example 45

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence ofMMAO (23% iso-butylaluminoxane

The procedure described in example 44 was followed except thepolymerization was conducted at 80° C. 1.4 g of a white rubbery solidwas isolated (400,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 0° C. ¹H NMR: 95 branches/1000 carbon atoms. GPC,:M_(n)=406,000; M_(w)/M_(n)=2.05.

Example 46

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence ofMMAO. (23% iso-butylaluminoxane)

The procedure described in Example 44 was followed except thepolymerization was conducted at 65° C. 2.15 g of a white rubbery solidwas isolated (630,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 15° C. ¹H NMR. 89 branches/1000 carbon atoms. GPC:M_(n)=502,000; M_(w)/M_(n)=1.78.

Example 47

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence ofMMAO(23% iso-butylaluminoxane

The procedure described in Example 44 was followed except thepolymerization was conducted at 25° C. 1.9 g of a white rubbery solidwas isolated (560,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 90° C. ¹H NMR: 33 branches/1000 carbon atoms. GPC:M_(n)=839,000; M_(w)/M_(n)=1.37.

Example 48 Oligomerization of ethylene to α-olefin with the nickeldibromide complex of 2,3-bis(phenylimino)-[1,4]dithiane in the presenceof MAO

A 1 L Fischer—Porter bottle was assembled onto a pressure head equippedwith a mechanical stirrer and gas and liquid feed-through ports, thenpressurized to 75 psig of ethylene and relieved to ambient pressureseven times. The bottle was immersed in a 21.5° C. water bath, then 50mL of dry, deoxygenated toluene was added via syringe, followed by 100μL of a stock solution of 15.3 mg of the nickel dibromide complex of2,3-bis(phenylimino)-[1,4]dithiane in 15.0 mL of dichloromethane,followed by another 50 mL of toluene. The mixture was stirred at 300 rpmunder 75 psig ethylene for 5 minutes to saturate the solution withethylene, then the pressure was relieved, and 4.0 mL of a 10 wt %solution of MAO in toluene was quickly added. The flask was immediatelyre-pressurized to 75 psig ethylene and stirred at 300 rpm. After 30minutes, the pressure was relieved and the reaction quenched by additionof 10 mL of methanol. After disassembling the apparatus, another 40 mLof methanol, 50 mL of 6 N aqueous HCl, and 10 mL acetone were added andthe mixture was stirred to complete hydrolysis of the MAO. The resultantorganic layer was separated, washed with 6 N aqueous HCl (1×25 mL), andwater (2×50 mL), then concentrated under reduced pressure (15 Torr) at40° C. to obtain an oil. This was treated with toluene (50 mL) andre-concentrated twice, then treated with acetone (50 mL) andre-concentrated, to obtain a waxy white polyethylene solid. Drying invacuo at 100° C., 250 mm Hg for 14 hours gave 0.180 g of polymer,approximate M_(n)=517, containing approximately 85% α-olefin and 15%internal olefin.

Example 49

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-2,3-dihydrobenzo[1,4]dithiine in thepresence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 100 mL of dry, deoxygenatedtoluene. The flask was placed in a water bath and allowed to equilibratewith 1 atmosphere ethylene for 10 minutes, then 0.25 mL of a stocksolution prepared from 10.2 mg of the nickel dibromide complex of2,3-bis-(2,6-dimethylphenylimino)-2,3-dihydrobenzo[1,4]dithiine in 13.11g dry, deoxygentated dichloromethane was added. The reaction mixture wasthen treated with 4.0 mL of a 10 wt % solution of MAO in toluene andstirred under 1 atmosphere ethylene. Ethylene uptake and formation of apolyethylene precipitate were observed. After 6.5 minutes, the mixturewas quenched by the addition of acetone (50 mL), methanol (50 mL) and 6N aqueous HCl (100 mL). The swollen polyethylene which separated wasisolated by vacuum filtration, then dried at 80° C. in vacuo for severalhours. 287 mg of a white powdery polyethylene was isolated (236,000TO/h). DSC: (2nd heat) melt with an endothermic maximum at 88° C. ¹H NMRshowed this material to contain approximately 36 branches/1,000 carbonatoms. GPC: M_(n)=145,000; M_(w)/M_(n)=2.35.

Example 50

Polymerization of ethylene using a catalyst formed in situ from2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and [Pd(NCCH₃)₄][BF₄]₂

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 0.022 g of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and 0.019 g[Pd(NCCH₃)₄][BF₄]₂. The flask was evacuated and refilled with ethylene,then 100 mL of dry, deoxygenated dichloromethane was added via syringeand the resultant mixture was stirred under 1 atmosphere of ethylene at25° C. Very little ethylene uptake was observed. After 10minutes, 0.412g B(C₆F₅)₃ was added, resulting in an increased rate of ethylene uptake.After a total of 84 minutes, the reaction was worked up by evaporatingthe dichloromethane under a stream of nitrogen, washing the residue withmethanol repeatedly to extract the B(C₆F₅)₃, and drying the residue invacuo to obtain 0.57 g of amorphous polyethylene, approximateM_(n)=17,000; M_(n)/M_(w)=1.3. ¹H NMR showed approximately 105 branchesper 1000 carbons.

Example 51

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(4-methoxy-2,6-dimethylphenylimino)-[1,4]dithiane in the presenceof MAO

A 500 mL round bottom flask fitted with a Schlenk adapter and equippedwith a magnetic stir bar and capped with a septum was evacuated,flame-dried, then refilled with ethylene. The flask was provided with aroom temperature (ca. 23° C.) water bath, then charged with 100 mL ofdry, deoxygenated toluene and allowed to equilibrate with 1 atmosphereethylene for 30 minutes. The reaction mixture was then treated with 4.0mL of a 10 wt % solution of MAO in toluene and stirred under 1atmosphere ethylene, then 0.10 mL of a stock solution (prepared from 6.3mg of the nickel dibromide complex of2,3-bis(4-methoxy-2,6-dimethylphenylimino)-[1,4]dithiane and 6.5 mLdichloromethane) was added. After 10 minutes, the reaction mixture wasquenched by the addition of acetone, methanol and 6 N aqueous HCl. Thepolyethylene which separated was isolated by vacuum filtration andwashed with water, methanol and acetone, dried on the filter for 2 h,then further dried 13 days in a vacuum oven at 80° C. 182 mg of a whitepolyethylene was isolated (254,000 TO/h). DSC: (2nd heat) melt with anendothermic maximum at 124° C. ¹H NMR: 13 branches/1000 carbon atoms.GPC: M_(n)=145,600; M_(w)/M_(n)=2.6.

Example 52

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence of(CH₃CH₂)₂AlCl

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 mL of toluene and 0.5 mL of a stock solution (10 mg in 10 mL CH₂Cl₂)of the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane. The autoclave washeated to 45° C. and 2 mL of (CH₃CH₂)₂AlCl (5000 equiv.) in toluene wasadded. The reactor was rapidly pressurized to 100 psig and thetemperature ramped up to 50° C. After 10 minutes at 50° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated by filtration and dried forseveral hours in a vacuum oven at 80° C. resulting in 1.9 g of a whiterubbery solid (560,000 TO/h). DSC: (2nd heat) broad melt with anendothermic maximum at 30° C. ¹H NMR: 87 branches/1000 carbon atoms.GPC: M_(n)=557,000; M_(w)M_(n)=1.82.

Example 53

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence of(CH₃CH₂)₂AlCl

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 mL of toluene and 0.5 mL of a stock solution (10 mg in 10 mL CH₂Cl₂)of the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane. The autoclave washeated to 45° C. and 0.2 mL of (CH₃CH₂)₂AlCl (500 equiv.) in toluene wasadded. The. reactor was rapidly pressurized to 100 psig and thetemperature ramped up to 50° C. After 10 minutes at 50° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated by filtration and dried forseveral hours in a vacuum oven at 80° C. resulting in 2 g of a whiterubbery solid (590,000 TO/h). DSC: (2nd heat) broad melt with anendothermic maximum at 30° C. ¹H NMR: 85 branches/1000 carbon atoms.GPC: M_(n)=515,000; M_(w)M_(n)=1.81.

Example 54

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane in the presence of(CH₃CH₂)₂AlCl

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 mL of toluene and 0.5 mL of a stock solution (10 mg in 10 mL CH₂Cl₂)of the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane. The autoclave washeated to 45° C. and 0.04 mL of (CH₃CH₂)₂AlCl (100 equiv.) in toluenewas added. The reactor was rapidly pressurized to 100 psig and thetemperature ramped up to 50° C. After 10 minutes at 50° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated by filtration and dried forseveral hours in a vacuum oven at 80° C. resulting in 1.5 g of a whiterubbery solid (440,000 TO/h). DSC: (2nd heat) broad melt with anendothermic maximum at 29° C. ¹H NMR: 80 branches/1000 carbon atoms.GPC: M_(n)=422,000; M_(w)M_(n)=1.97.

Example 55 Copolymerization of ethylene and ethyl undecenoate with thenickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of MMAO(23% iso-butylaluminoxane)

A flame dried Schlenk flask equipped with a stir bar and a rubber septumwas charged with 50 ml of toluene and 5 mg of the nickel dibromidecomplex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane. The flask wascooled to 0° C. in an ice-water bath and filled with ethylene (1atmosphere). To the flask was added 2.0 ml of MMAO in heptane (6.42 wt %aluminum). Within 5 seconds, 5 ml of ethyl undecenoate was added to givea purple solution. The mixture was left to stir for 16 hours. Acetone,methanol and 6M HCl were added to quench the reaction and precipitatethe polymer. The polymer was collected by suction filtration and washedwith copious amounts of acetone to ensure all of the ethyl undecenoatecomonomer was removed resulting in 100 mg of white powdery polymer. NMRspectroscopic analysis is consistent with the preparation of an estergroup containing copolymer. In addition, ethylene homopolymer, whichresulted from the short reaction time prior to addition of the ethylundecenoate, was present. ¹H NMR: 7.5 wt % ethyl undecenoateincorporated. GPC: M_(n)=9500, M_(w)/M_(n)=16.6. DSC: T_(m)=128° C.

Example 56 Co-polymerization of ethylene and 1,13-tetradecadiene withthe nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was flame-dried under vacuum, refilled withethylene, and then sequentially charged with 50 mL of dry, deoxygenatedtoluene, 6.0 mL of deoxygenated 1,13-tetradecadiene, and 1.0 mL of astock solution of 11.8 mg of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in 10.0 mL of dry,deoxygenated dichloromethane. The flask was placed in a 23° C. waterbath and allowed to equilibrate with 1 atmosphere of ethylene for 5minutes, then 4.0 mL of a 10 wt % solution of MAO in toluene was addedand the mixture was stirred under 1 atmosphere of ethylene. Ethyleneuptake was observed and the mixture rapidly became more viscous. After 7minutes, the reaction was quenched by the addition of acetone (50 mL),methanol (50 mL) and 6 N aqueous HCl (100 mL). The co-polymer whichseparated was isolated by vacuum filtration and dried in vacuo at 100°C. for 24 hours to obtain 0.72 g of a rubbery white polymer, whichformed a gel upon attempted re-dissolution in hot o-dichlorobenzene.

Example 57

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 3.4 mg of the nickel dibromidecomplex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane The flask wasevacuated and refilled with ethylene, then charged with 75 mL of dry,deoxygenated toluene. The resultant suspension was cooled to 0° C. andallowed to equilibrate with 1 atmosphere ethylene for 15 minutes, thentreated with 4.0 mL of a 10 wt % solution of MAO in toluene and stirredunder 1 atmosphere ethylene. A white polyethylene precipitate (with afaint yellow-orange tinge) was observed within minutes. After 38minutes, the mixture was quenched by the addition of acetone (50 mL),methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen polyethylenethat separated was isolated by vacuum filtration and washed with water,methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg)for 18 hours to give 6.0 g of a white polyethylene (54,000 TO/h). ¹HNMR: 19 branches/1000 carbon atoms. GPC: M_(n)=504,000; M_(w)/M_(n)=2.3.

Example 58

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(benzyloxymethyl)-5,6-bis(2,6-dimethylphenylimino)[1,4]dioxane inthe presence of MAO

A 500 mL round bottom flask was fitted with a Schlenk adapter andequipped with a magnetic stir bar and capped with a septum was chargedwith 100 mL of dry, deoxygenated toluene. The flask was placed in awater bath and allowed to equilibrate with 1 atmosphere ethylene for 19minutes, then 0.25 mL of a stock solution prepared from 10.0 mg of thenickel dibromide complex of2,3-bis(benzyloxymethyl)-5,6-bis(2,6-dimethylphenylimino)-[1,4]dioxaneand 10.0 mL dichloromethane was added. The reaction mixture was thentreated with 4.0 mL of a 10 wt % solution of MAO in toluene and stirredunder 1 atmosphere ethylene. Ethylene uptake and formation of apolyethylene precipitate were observed. After 6.5 minutes, the mixturewas quenched by the addition of acetone, methanol and 6 N aqueous HCl.The swollen polyethylene which separated was isolated by vacuumfiltration, then dried at 80° C. in vacuo for several hours. 392 mg ofwhite polyethylene was isolated (404,000 TO/h). DSC: (2nd heat) meltwith an endothermic maximum at 120° C. ¹H NMR: 16 branches/1000 carbonatoms. GPC: M_(n)=125,000; M_(w)/M_(n)=2.8.

Example 59

Polymerization of ethylene with the nickel dibromide complex of5-methoxymethyl-2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in thepresence of MAO

A 200 mL pear-shaped Schlenk flask, equipped with a magnetic stir barand,capped with a septum was charged with 3.8 mg of the nickel dibromidecomplex of 5-methoxymethyl-2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxaneThe flask was evacuated and refilled with ethylene, then charged with 75mL of dry, deoxygenated toluene. The resultant suspension was cooled to0° C. and allowed to equilibrate with 1 atmosphere ethylene for 15minutes, then treated with 4.0 mL of a 10 wt % solution of MAO intoluene and stirred under 1 atmosphere ethylene. After 10 minutes, themixture was quenched by the addition of acetone (50 mL), methanol (50mL) and 6 N aqueous HCl (100 mL). The swollen polyethylene whichseparated was isolated by vacuum filtration and washed with water,methanol and acetone, then dried under reduced pressure (0.05-0.1 mm Hg)for 48 hours to give 1.04 g of a white, powdery polyethylene. A similarreaction, also at 0° C., was conducted using 0.655 g (equivalent to 0.57mg of the nickel complex) of a stock solution of 11.6 mg nickeldibromide complex of5-methoxymethyl-2,3-bis-(2,6-dimethylphenylimino)-[1,4]dioxane in 13.238g dichloromethane to obtain 291 mg white, powdery polyethylene after 15minutes reaction.

Example 60

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 mL of toluene and 0.3 mL of a stock solution (10 mg in 10 mL CH₂Cl₂)of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane The autoclave was heatedto 60° C. and 2 mL of MMAO in heptane (6.42 wt % aluminum) was added.The reactor was rapidly pressurized to 100 psig and the temperatureramped up to 65° C. After 10 minutes at 65° C., the reaction wasquenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated by filtration and dried forseveral hours in a vacuum oven at 80° C. 1.3 g of a white rubbery solidwas isolated (480,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 76° C. ¹H NMR: 33 branches/1000 carbon atoms. GPC: Mn=42,000;Mw/Mn=1.82.

Example 61

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

The procedure described in example 60 was followed except thepolymerization was conducted at 25° C. resulting in 0.59 g ofpolyethylene (226,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 125° C. ¹H NMR: 9 branches/1000 carbon atoms. GPC:Mn=237,000; Mw/Mn=2.15.

Example 62

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2.6-dimethylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

The procedure described in example 60 was followed except thepolymerization was conducted at 80° C. resulting in 0.29 g ofpolyethylene (110,000 TO/h). ¹H NMR: 69 branches/1000 carbon atoms. GPC:Mn=23,000; Mw/Mn=1.65.

Example 63

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4 dioxane in the presence of MMAO(23% iso-butylaluminoxane)

The procedure described in example 60 was followed except thepolymerization was conducted at 50° C. resulting in 3.1 g ofpolyethylene (1,2007000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 95° C. ¹H NMR: 48 branches/1000 carbon atoms. GPC: Mn=63,000;Mw/Mn=1.92.

Example 64

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 mL of toluene and 0.5 mL of a stock solution (10 mg in 10 mL CH₂Cl₂)of the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane The autoclave washeated to 60° C. and 2 mL of MMAO in heptane (6.42 wt % aluminum) wasadded. The reactor was rapidly pressurized to 100 psig and thetemperature ramped up to 65° C. After 10 minutes at 65° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated by filtration and dried forseveral hours in a vacuum oven at 80° C. 2.5 g of a white rubbery solidwas isolated (660,000 TO/h). DSC: (2nd heat) broad melt with anendothermic maximum at 30° C. ¹H NMR: 82 branches/1000 carbon atoms.GPC: Mn=147,000; MwMn=1.91.

Example 65

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

The procedure described in example 64 was followed except thepolymerization was conducted at 50° C. resulting in 3.4 g ofpolyethylene (900,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 50° C. ¹H NMR: 65 branches/1000 carbon atoms. GPC:Mn=219,000; Mw/Mn=1.85.

Example 66

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

The procedure described in example 64 was followed except thepolymerization was conducted at 25° C. resulting in 1.22 g ofpolyethylene (320,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at 112° C. ¹H NMR: 17 branches/1000 carbon atoms. GPC:M_(n)=476,000; M_(w)/M_(n)=2.02.

Example 67

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

The procedure described in example 64 was followed except thepolymerization was conducted at 80° C. resulting in 0.9 g ofpolyethylene (240,000 TO/h). DSC: (2nd heat) melt with an endothermicmaximum at −10° C. ¹H NMR: 99 branches/1000 carbon atoms. GPC:Mn=98,800; Mw/Mn=1.81.

Example 68 Copolymerization of ethylene and ethyl undecenoate with thenickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane in the presence of MMAO(23% iso-butylaluminoxane)

A flame dried Schlenk flask equipped with a stir bar and a rubber septumwas charged with 50 ml of toluene and 6 mg of the nickel dibromidecomplex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane The flask wascooled to 0° C. in an ice-water bath and filled with ethylene (1atmosphere). To the flask was added, 2.0 ml of MMAO in heptane (6.42 wt% aluminum). Within 15 seconds 2.5 ml of ethyl undecenoate was added togive a purple solution. The mixture was left to stir for 16 hours.Acetone, methanol and 6M HCl were added to quench the reaction andprecipitate the polymer. The polymer was collected by suction filtrationand washed with copious amounts of acetone to ensure all of the ethylundecenoate comonomer is removed resulting in 510 mg of white powderypolymer. NMR spectroscopic analysis is consistent with the preparationof an ester group containing copolymer. In addition, ethylenehomopolymer, which resulted from the short reaction time prior toaddition of the ethyl undecenoate, was present. IR: CO stretch at 1742cm⁻¹. ¹H NMR: 1.0 wt % ethyl undecenoate incorporated. GPC:M_(n)=61,000, M_(w)/M_(n)=6.4. DSC: T_(m)=125° C.

Example 69

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-4-methylmorpholine in the presenceof MAO

A 1 L Fischer-Porter bottle was assembled onto a pressure head equippedwith a mechanical stirrer and gas and liquid feed-through ports, thenpressurized to 75 psig of ethylene and relieved to ambient pressureseven times. The bottle was immersed in a 54° C. water bath, then 100 mLof dry, deoxygenated toluene was added via syringe. The mixture wasre-pressurized with ethylene at 75 psig and stirred at 300 rpm for 5minutes to saturate the solution with ethylene, then the pressure wasagain relieved, and 4.0 mL of a 10 wt % solution of MAO in toluene wasquickly added. The apparatus was again re-pressured to 75 psig ethyleneand stirred at 300 rpm for another 5 min to ensure saturation withethylene. The pressure was once again relieved to ambient pressure and0.5 mL of a stock solution prepared from 10.0 mg of the nickel dibromidecomplex of 2,3-bis(2,6-diisopropylphenylimino)-4-methylmorpholine and 10mL dichloromethane was quickly added and the system quickly pressurizedonce again with ethylene to 75 psig. After 7 min the pressure wasrelieved to atmospheric and the reaction was quenched by addition of 5mL methanol. After the apparatus was disassembled, an additional 50 mLmethanol, 50 ml aqueous 6N HCl and 20 mL acetone was added. Theresultant organic layer was separated, washed with 6 N aqueous HCl (1×25mL), and water (2×50 mL), then concentrated by rotary evaporation underreduced pressure (10 Torr) at 40° C. The residue was then treated withtoluene (50 mL) and re-concentrated to afford 134 mg of a very rubbery,clear polyethylene (55,000 TO/h). ¹H NMR: 134 branches/1000 carbonatoms. GPC: M_(n)=169,000; M_(w)/M_(n)=1.4.

Example 70

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethyl-phenylimino)-4-methylmorpholine in the presence ofMMAO

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with1510 mL of toluene and 1 mL of a stock solution (10 mg in 20 mL CH₂Cl₂)of the nickel dibromide complex of2,3-bis(2,6-dimethyl-phenylimino)-4-methylmorpholine. The autoclave washeated to 45° C. and 3 mL of MMAO in heptane (6.42 wt % aluminum) wasadded. The reactor was rapidly pressurized to 100 psig and thetemperature ramped up to 50° C. After 10 minutes at 50° C., the reactionwas quenched by the addition of acetone, and methanol. The swollenpolyethylene which separated was isolated by filtration and dried forseveral hours in a vacuum oven at 80° C. resulting in 0.87 g of a whiterubbery solid was isolated (138,000 TO/h). ¹H NMR: 97 branches/1000carbon atoms.

Example 71

Polymerization of ethylene with the nickel dibromide complex of1,3-bis(4-methoxy-2,6-dimethyl phenyl)-45-bis(4-methoxy-2,6-dimethylphenylimino)imidazolidin-2-one in thepresence of MAO

A 500 mL round bottom flask fitted with a Schlenk adapter and equippedwith a magnetic stir bar and capped with a septum was evacuated,flame-dried, then refilled with ethylene. The flask was provided with aroom temperature (ca. 23° C.) water bath, then charged with 100 mL ofdry, deoxygenated toluene and allowed to equilibrate with 1 atmosphereethylene for 30 minutes while stirring at 1000 rpm. The reaction mixturewas then treated with 4.0 mL of a 10 wt % solution of MAO in toluene andstirred under 1 atmosphere ethylene, then 0.10 mL of a stock solutionprepared from 6.0 mg of the nickel dibromide complex of1,3-bis(4-methoxy-2,6-dimethylphenyl)-4,5-bis(4-methoxy-2,6-dimethylphenylimino)imidazolidin-2-one and 6.0 mLdichloromethane was added. After about 7 min and 20 seconds anadditional 0.25 mL of the stock solution was added. After 15 moreminutes, the reaction mixture was quenched by the addition of acetone,methanol and 6 N aqueous HCl. The polyethylene which separated wasisolated by vacuum filtration and washed with water, methanol andacetone, then dried on the filter for 2 h, then further dried 13 days ina vacuum oven at 80° C. to obtain 172 mg white polyethylene. DSC: (2ndheat) melt with an endothermic maximum at 124° C. ¹H NMR showed thismaterial to contain approximately 18 branches/1000 carbon atoms. GPC:M_(n)=56,500; M_(w)/M_(n)=3.55.

Example 72

Polymerization of ethylene with the reaction product of1,3-bis-(2,6-dimethyl-phenyl)-4,5-bis-(2,6-dimethyl-phenylimino)-imidazolidin-2-one,(1,2-dimethoxyethane)nickel(II) dibromide, and silver tetrafluoroboratein the presence of MAO

A 500 mL round bottom flask fitted with a Schlenk adapter, capped with aseptum, and equipped with a magnetic stir bar was charged with 100 mL ofdry, deoxygenated toluene. The flask was placed in a water bath andallowed to equilibrate with 1 atmosphere ethylene for 10 minutes, then0.10 mL of a stock solution (freshly prepared from 240 mg of thereaction product of1,3-bis-(2,6dimethylphenyl)-4,5-bis-(2,7,6-dimethylphenylimino)-imidazolidin-2-one,(1,2-dimethoxyethane)nickel(II) dibromide, and silver tetrafluoroboratein 10 mL dry, deoxygentated dichloromethane) was added. The reactionmixture was then treated with 4.0 mL of a 10 wt % solution of MAO intoluene and stirred under 1 atmosphere ethylene. Ethylene uptake andformation of a polyethylene precipitate were observed. After 6.33minutes, the mixture was quenched by the addition of acetone (50 mL),methanol (50 mL) and 6 N aqueous HCl (100 mL). The swollen polyethylenewhich separated was isolated by vacuum filtration, then dried at 80° C.in vacuo for several hours. 860 mg of a white powdery polyethylene wasisolated (87,000 TO/h). ¹H NMR: 15 branches/1000 carbon atoms. GPC:M_(n)=76,000; M_(w)/M_(n)=2.6

Example 73

Polymerization of ethylene using a catalyst generated in situ fromtetrakis(2,6-dimethylphyenl)oxalamidine,bis(1,5-cyclooctadiene)nickel(O) and HB(Ar)₄(Ar=3,5-bis(trifluoromethyl)phyenl)

A 250 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 8.0 mg ofbis(1,5-cyclooctadiene)nickel(O), 19 mg of N¹,N²,N³,N⁴-tetrakis(2,6-dimethylphenyl)oxalamidine, and 33 mg of the ethersolvate of HB(Ar)₄. The flask was evacuated and refilled with ethylene,then charged with 75 mL of dry, deoxygenated toluene. The yellowsolution which resulted was stirred under ethylene at 0° C. for 30minutes, then warmed to 25° C. and stirred for another 30 minutes underethylene before being quenched by addition of acetone (50 mL), andmethanol (50 mL). The polyethylene which separated was isolated byvacuum filtration and washed with water, methanol and acetone, thendried under reduced pressure (0.5 mm Hg) for 14 hours to give 0.70 g ofan elastic white polyethylene (average 860 TO/h). ¹H NMR: 83branches/1000 carbon atoms. GPC: M_(n)=173,000; M_(w)M_(n)=2.8.

Example 74

Polymerization of ethylene with the nickel dibromide complex of1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine in the presenceof MAO

A 250 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 10.4 mg of the nickel dibromidecomplex of 1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine. Theflask was evacuated and refilled with ethylene, then charged with 75 mLof dry, deoxygenated toluene. The resultant suspension was cooled to 0°C. and allowed to equilibrate with 1 atmosphere ethylene for 15 minutes,then treated with 4.0 mL of a 10 wt % solution of MAO in toluene. Theyellow solution which resulted was stirred under ethylene at 0° C. for 1hour, and then quenched by the addition of acetone (50 mL), methanol (50mL) and 6 N aqueous HCl (100 mL). The swollen polyethylene whichseparated was isolated by vacuum filtration and washed with water,methanol and acetone, then dried under reduced pressure (0.5 mm Hg) for14 hours to give 1.3 g of a clear elastic polyethylene (2531 TO/h). ¹HNMR: 91 branches/1000 carbon atoms. GPC: M_(n)=127,000; M_(w)/M_(n)=1.3.

Example 75 Ethylene Polymerization Using Complex XXXV

A flame dried Schlenk flask equipped with a stir bar and a rubber septumwas charged with 50 ml of methylene chloride and 50 mg of the palladiumcomplex XXXV. The flask was placed under an ethylene atmosphere (1atmosphere). The mixture was left to stir for 20 hours. Acetone andmethanol were added to quench the reaction and precipitate the polymer.The polymer was collected and dried in vacuo resulting in 2.6 g of tackypolymer. NMR spectroscopic analysis is consistent with the preparationof an ethylene homopolymer. ¹H NMR: highly branched polyethylene. GPC:M_(n)=34,000, M_(w)/M_(n)=2.5. DSC: T_(m)=−39° C., T_(g)=−69° C.

Example 76

Propylene Polymerization Using Complex XXXV

A flame dried Schlenk flask equipped with a stir bar and a rubber septumwas charged with 50 ml of methylene chloride and 50 mg of the palladiumcomplex XXXV. The flask was placed under a propylene atmosphere (1atmosphere). The mixture was left to stir for 20 hours. Acetone andmethanol were added to quench the reaction and precipitate the polymer.The polymer was collected and dried in vacuo resulting in 580 mg oftacky polymer. ¹H NMR: 192 branch points/1000 carbon atoms. GPC:M_(n)=17,000, M_(w)/M_(n)=2.08. DSC: T_(g)=−53° C.

Example 77 Ethylene/vinyl Ethylene Carbonate Copolymerization UsingComplex XXXV

A 200 mL flame dried pear-shaped Schlenk flask equipped with a magneticstir bar and capped with a septum was charged with(2,6-di-isopropylphenylimino)-[1,4]dithiane Pd(II) catalyst XXXV (100mg) in an argon filled glove box. Upon removal from the glove box, theflask was evacuated and backfilled with ethylene. The catalyst wasdissolved in CH₂Cl₂ (25 mL) and immediately treated with vinyl ethylenecarbonate (5 mL). The resulting orange solution was stirred at 23° C.under an ethylene atmosphere (1 atm) for 20 hours. A small amount ofpolymer had precipitated out of solution. The polymerization wasquenched with MeOH and acetone leaving gray oil adhering to the walls ofthe flask. The polymer was washed several times with acetone and MeOH toremove any remaining monomer. The polymer was dissolved in CH₂Cl₂ andtransferred to a storage jar. The solvent was left to evaporate and theresulting oily polymer was dried in vacuo at ˜80° C. for 3 days toafford a tacky solid (2.15 g, 1100 TO). ¹H NMR was consistent with acopolymer containing approximately 96.5 weight % ethylene and 3.5 weight% vinyl ethylene carbonate monomer units.; M_(n)40,200^(g)/_(mol); M_(w)92,100^(g)/_(mol); DSC T_(g)−68° C., T_(m)−38° C.

Example 78 Ethylene/vinyl Ethylene Carbonate Copolymerization UsingComplex XXXV

A 200 mL flame dried pear-shaped Schlenk flask equipped with a magneticstir bar and capped with a septum was charged with(2,6-di-isopropylphenylimino)-[1,4]dithiane Pd(II) catalyst XXXV (100mg) in an argon filled glove box. Upon removal from the glove box, theflask was evacuated and backfilled with ethylene. The catalyst wasdissolved in CH₂Cl₂ (20 mL) and immediately treated with vinyl ethylenecarbonate (10 mL). The resulting orange solution was stirred at 23° C.under an ethylene atmosphere (1 atm) for 28 hours. A small amount ofpolymer had precipitated out of solution. The polymerization wasquenched with MeOH and acetone leaving gray oil adhering to the walls ofthe flask. The polymer was dissolved in CH₂Cl₂ and transferred to astorage jar. The solvent was left to evaporate and the resulting oilypolymer was washed several times with acetone and MeOH to remove anyremaining monomer and dried in vacuo at ˜80° C. for 1 day to afford atacky solid (1.15 g, 613 TO). ¹H NMR was consistent with a copolymercontaining approximately 95.5 weight % ethylene and 4.5 weight % vinylethylene carbonate monomer units.; M_(n)15,400^(g)/_(mol); M_(w)96,000^(g)/_(mol); DSC T_(g)−64° C., T_(m)−31° C.

Example 79

Preparation of the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane

A Schlenk flask equipped with a magnetic stir bar was charged with 100mg of 2,3-bis(2,6-diisopropylphenylimino)-[1,4]dioxane (0.25, mmol) and71 mg of (1,2-dimethoxyethane)nickel(II) dibromide (0.23 mmol) under anargon atmosphere. Dry, deoxygenated dichloromethane (15 mL) was addedand the mixture was stirred under an argon atmosphere, turning red-brownwithin about 10 minutes. After 2 hours, the red/orange solution wastransferred via filter cannula to a new flame dried Schlenk to removetrace amount of unreacted (1,2-dimethoxyethane)nickel(II) dibromide. TheCH₂Cl₂ was removed in vacuo. The resulting red-brown solid was washedwith 2×10 mL of hexane and the solid was dried in vacuo for severalhours affording 80 mg of a brown solid.

Example 80

Preparation of2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazor2,1-b]thiazole

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet was charged with 752 mg ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 200 mg of sodiumhydride (60% mineral oil dispersion), 5.0 mL of dry tetrahydrofuran, and250 mg of 2-mercaptoimidazole. The mixture was heated at reflux for 120minutes. After cooling, the mixture was diluted with water anddichloromethane, and the organic layer was separated and concentrated toafford a yellow-orange oil. Column chromatography (SiO₂, Merck Grade9385 230-400 mesh, 60 Å; 12 v % ethyl acetate in hexane) afforded 487 mgof a yellow-orange solid. Recrystallization from heptane gave 366 mgyellow-orange prisms. Field desorption mass spectrometry showed a parention peak at 360 m/z.

Example 81

Preparation of N¹,N²bis(2,6-dimethylphenyl)ethanediimidoselenoic aciddiphenyl ester

A 50 mL round bottom flask equipped with a magnetic stir bar and areflux condenser capped by a nitrogen inlet was charged with 961 mg ofN¹,N²-bis(2,6-dimethylphenyl)oxalodiimidoyl dichloride, 287 mg of sodiumhydride (60% mineral oil dispersion), 8.2 mL of dry tetrahydrofuran, and0.068 mL of benzeneselenol. The mixture was heated at reflux for 45minutes. After cooling, the mixture was diluted with water and diethylether. The ether layer was separated and washed again with water, thenconcentrated in vacuo to afford a yellow-orange crystalline solid. Thesolid was dissolved in hot hexane, then filtered, and thenreconcentrated. Recrystallization from heptane afforded 745 mg orangeprisms, 1^(st) crop. Field desorption mass spectrometry showed a parention cluster of peaks from 570-578 m/z. ¹H NMR (300 MHz, CDCl₃, chemicalshifts in ppm relative to TMS at 0 ppm): 1.95 (12 p, s), 6.75 (6p, apps), 7.02-7.20 (6p, m), 7.39-7.48 (4p, m).

Example 82

Polymerization of ethylene using a catalyst generated in situ fromN¹,N²-bis(2,6-dimethylphyenl)ethanediimidoselenoic acid diphenyl ester,bis(1,5-cyclooctadiene)nickel(O) and HB(Ar)₄(Ar=3,5-bis(trifluoromethyl)phenyl)

A 250 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 5 mg ofbis(1,5-cyclooctadiene)nickel(O), 10 mg ofN¹,N²-bis(2,6-dimethylphenyl)ethanediimidoselenoic acid diphenyl ester,and 25 mg of the ether solvate of HB(Ar)₄. The flask was evacuated andrefilled with ethylene, then charged with 45 mL of dry, deoxygenatedtoluene. The yellow solution which resulted was stirred under ethyleneat 21° C. for 10 minutes, then quenched by addition of methanol (50 mL).The polyethylene which separated was isolated by vacuum filtration andwashed with methanol, then dried under reduced pressure (0.5 mm Hg) for14 hours to give 0.060 g of an elastic blue-green polyethylene. ¹H NMR:24 branches/1000 carbon atoms. GPC: M_(n)=181,000; M_(w)/M_(n)=3.5.

Example 83

Preparation of the nickel dibromide complex of2,3-bis(2.6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazole

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 141 mg of2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1′-b]thiazole and110 mg of (1,2-dimethoxyethane)nickel(II) dibromide under an inertatmosphere. Dry, deoxygenated dichloromethane (5 mL) was added and themixture was stirred under an argon atmosphere. After 1 hour, another 5mL of dichloromethane was added. The mixture was stirred another 16hours at 21° C., then diluted with 10 mL of dry, deoxygenated hexane andstirred another 3 hours. The supernatant was removed via a filterpaper-tipped cannula, and the residue dried in vacuo at 1 mm Hg toafford 66 mg of a brown microcrystalline solid.

Example 84

Polymerization of ethylene with the nickel dibromide complex2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazole inthe presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 2.5 mg of the nickel dibromidecomplex of2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazole. Theflask was evacuated and refilled with ethylene, then charged with 75 mLof dry, deoxygenated toluene. The resultant suspension allowed toequilibrate with 1 atmosphere ethylene at 21° C. for 15 minutes, thentreated with 200 μL of a 10 wt % solution of MAO in toluene and stirredunder 1 atmosphere ethylene. After 21 min, the reaction was quenched bythe addition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl(100 mL). The swollen polyethylene which separated was isolated byvacuum filtration and washed with water, methanol and acetone, thendried under reduced pressure (0.05-0.1 mm Hg) for 24 hours to give 198mg of a white polyethylene. ¹H NMR: 13 branches/1000 carbon atoms. GPC:bimodal, with M_(n)=23,000; M_(p)=366,000; M_(w)/M_(n)=13.5.

Example 85

Preparation of the nickel dibromide complex ofN¹,N²,N³,N⁴-tetrakis(2,6-dimethylphenyl)oxalamidine

A 50 mL Schlenk flask equipped with a magnetic stir bar and capped witha septum was charged with 100 mg ofN¹,N²,N³,N⁴-tetrakis(2,6-dimethylphenyl)oxalamidine and 55 mg of(1,2-dimethoxyethane)nickel(II) dibromide under an inert atmosphere.Dry, deoxygenated dichloromethane (5 mL) was added and the mixture wasstirred under an argon atmosphere. After 1 hour, another 5 mL ofdichloromethane was added. The mixture was stirred another 16 hours at21° C., then diluted with 10 mL of dry, deoxygenated hexane and stirredanother 3 hours. The supernatant was removed via a filter paper-tippedcannula, and the residue dried in vacuo at 1 mm Hg to afford 95 mg oflight green crystals.

Example 86

Polymerization of ethylene with the nickel dibromide complex ofN¹,N²,N³,N⁴-tetrakis(2,6-dimethylphyenl)oxalamidine in the presence ofMAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 2.4 mg of nickel dibromide complexof N¹,N²,N³,N⁴-tetrakis(2,6-dimethylphenyl)oxalamidine. The flask wasevacuated and refilled with ethylene, then charged with 75 mL of dry,deoxygenated toluene. The resultant suspension allowed to equilibratewith 1 atmosphere ethylene at 21° C. for 15 minutes, then treated with4.0 mL of a 10 wt % solution of MAO in toluene and stirred under 1atmosphere ethylene. After 30 min, the reaction was quenched by theaddition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl (100mL). The swollen polyethylene which separated was isolated by vacuumfiltration and washed with water, methanol and acetone, then dried underreduced pressure (0.05-0.1 mm Hg) for 24 hours to give 743 mg of a whitepolyethylene. ¹H NMR: 112 branches/1000 carbon atoms. GPC:M_(n)=330,000; M_(w)/M_(n)=1.4.

Example 87 Copolymerization of ethylene and 1-pentene with the nickeldibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane inthe presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 0.5 mL of a stock solution of 12.4mg of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in 10.0 mLdichloromethane. The flask was evacuated and refilled with ethylene,then charged with 100 mL of dry, deoxygenated toluene, and 5.0 mL1-pentene. The resultant suspension was cooled to 0° C. and allowed toequilibrate with 1 atmosphere ethylene for 15 minutes, then treated with4.0 mL of a 10 wt % solution of MAO in toluene and stirred under 1atmosphere ethylene. After 45 minutes, the mixture was quenched by theaddition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl (100mL). The swollen copolymer which separated was isolated by vacuumfiltration and washed with water, methanol and acetone, then dried underreduced pressure (255 mm Hg) at 100° C. for 24 hours to obtain 2.0 g ofwhite coploymer. ¹H NMR: 24 branches/1000 carbon atoms. ¹³C NMR: 7.6methyl branches/1000 carbons, 1.2 ethyl branches/1000 carbons, 9.1propyl branches/1000 carbons, 2.1 butyl branches/1000 carbons, 3.4pentyl and higher alkyl branches/1000 carbons. GPC: M_(n)=274,000;M_(w)/M_(n)=2.3.

Example 88 Copolymerization of ethylene and 1-heptene with the nickeldibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane inthe presence of MAO

A 200 mL pear-shaped Schlenk flask equipped with a magnetic stir bar andcapped with a septum was charged with 0.5 mL of a stock solution of 12.4mg of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in 10.0 mLdichloromethane. The flask was evacuated and refilled with ethylene,then charged with 100 mL of dry, deoxygenated toluene, and 5.0 mL1-heptene. The resultant suspension was cooled to 0° C. and allowed toequilibrate with 1 atmosphere ethylene for 15 minutes, then treated with4.0 mL of a 10 wt % solution of MAO in toluene and stirred under 1atmosphere ethylene. After 33 minutes, the mixture was quenched by theaddition of acetone (50 mL), methanol (50 mL) and 6 N aqueous HCl (100mL). The swollen copolymer which separated was isolated by vacuumfiltration and washed with water, methanol and acetone, then dried underreduced pressure (255 mm Hg) at 100° C. for 24 hours to obtain 1.25 g ofwhite coploymer. ¹H NMR: 19 branches/1000 carbon atoms. ¹³C NMR: 5.9methyl branches/1000 carbons, less than 1 ethyl branch/1000 carbons,less than 1 propyl branch/1000 carbons, 1.8 butyl branches/1000 carbons,11.5 pentyl and higher alkyl branches/1000 carbons. GPC: M_(n)=223,000;M_(w)/M_(n)=2.3.

Example 89

Polymerization of 1-hexene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence of MAO

A 22 mL vial equipped with a magnetic stir bar and capped by a septumwas sequentially charged with 1.8 mg of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane, 4.0 mL 1-hexene, and 2.0mL of a 10 wt % solution of MAO in toluene, under Ar. The resultantviolet mixture thickened noticably within minutes. After 34 min, thereaction was quenched with acetone, methanol and 6 N aq HCl, and thepolyhexene which separated was filtered off and dried in vacuo (0.4 mmHg) to obtain 428 mg of an elastic polyhexene. ¹H NMR: 173 branches/1000carbon atoms. GPC: M_(n)=92,000; M_(w)/M_(n)=2.0.

Example 90

Polymerization of 1-hexene with the nickel dibromide complex2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazole inthe presence of MAO

A 22 mL vial equipped with a magnetic stir bar and capped by a septumwas sequentially charged with 2.1 mg of the nickel dibromide complex2,3-bis(2,6-dimethylphenylimino)-2,3-dihydroimidazo[2,1-b]thiazole, 4.0mL 1-hexene, and 2.0 mL of a 10 wt % solution of MAO in toluene, underAr. The resultant dark purple-brown mixture thickened noticably within10-20 minutes. After 53 min, the reaction was quenched with acetone,methanol and 6 N aq HCl, and the polyhexene which separated was filteredoff and dried in vacuo (0.4 mm Hg) to obtain 283 mg of an elasticpolyhexene. ¹H NMR: 110 branches/1000 carbon atoms. GPC: M_(n)=91,000;M_(w)/M_(n)=1.9.

Example 91

Polymerization of 1-hexene with the nickel dibromide complex of1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine in the presenceof MAO

A 22 mL vial equipped with a magnetic stir bar and capped by a septumwas sequentially charged with 2.1 mg of nickel dibromide complex of1,4-dimethyl-2,3-bis(2,6-dimethylphenylimino)piperazine, 4.0 mL1-hexene, and 2.0 mL of a 10 wt % solution of MAO in toluene, under Ar.The resultant clear yellow solution was stirred at 23° C. for 400 min,then the reaction was quenched with acetone, methanol and 6 N aq HCl,and the polyhexene which separated was filtered off and dried in vacuo(0.4 mm Hg) to obtain 408 mg of an elastic polyhexene. ¹H NMR: 90branches/1000 carbon atoms. GPC: M_(n)=47,000; M_(w)/M_(n)=1.7.

Example 92 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 30 mg (52 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 25 mL of the CH₂Cl₂ was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour thesolvent was removed in vacuo. The resulting purple solid was washed withCH₂Cl₂ using a filter cannula and dried under dynamic vacuum.

Example 93 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 15 mg (26 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 20 mL of toluene was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour the solidwas allowed to settle and the solvent was removed via filter cannula.The resulting purple solid was washed with toluene using a filtercannula. The resulting purple silica support material was dried underdynamic vacuum giving 916 mg of supported catalyst material.

Example 94 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 30 mg (52 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 20 mL of toluene was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour the solidwas allowed to settle and the solvent was removed via filter cannula.The resulting purple solid was washed with toluene using a filtercannula and was dried under dynamic vacuum giving 900 mg of supportedcatalyst material.

Example 95 Synthesis of the supported nickel complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 34 mg (50 μmol) of the nickel dibromide complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane and 1 g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 20 mL of CH₂Cl₂ was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour thesolvent was removed in vacuo. The resulting red brown solid was washedwith CH₂Cl₂ using a filter cannula and dried under dynamic vacuum giving780 mg of supported catalyst.

Example 96 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino-)[1,4]dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 15 mg (26 μmol) of the nickel dibromide complex, of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 20 mL of CH₂Cl₂ was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour thesolvent was removed in vacuo resulting in 940 mg of a purple solid.

Example 97

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 92

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 100 mg of the nickel/MAO treated silica supportedcatalyst system prepared in example 92. The flask was placed under anethylene atmosphere and 50 mL of toluene was added giving a red/brownsuspension. The polymerization was left to stir for 1 hour at 23° C.After 60 minutes at 23° C., the reaction was quenched by the addition ofacetone, 6M HCl and methanol. The swollen polyethylene was isolated byfiltration and dried for several hours in a vacuum oven at 100° C.resulting in 1.6 g of a white rubbery solid (11,000 TO/h based on 100%active catalyst). DSC: (2nd heat) melt with an endothermic maximum at118° C. ¹H NMR: 30 branches/1000 carbon atoms. GPC: M_(n)=208,000;MwMn=2.45.

Example 98

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 92

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 200mg of the supported catalyst prepared in example 92. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 60° C. The reactor was rapidly pressurized to 90 psig ethylene. After 60 minutes at 60° C., the reaction was quenched by the additionof acetone, 6M HCl and methanol. The swollen polyethylene was isolatedby filtration and dried for several hours in a vacuum oven at 100° C.resulting in 22.5 g of a white rubbery solid (80,000 TO/h). ¹H NMR: 31branches/1000 carbon atoms. GPC: M_(n)=128,000; Mw/Mn=2.58.

Example 99

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 92

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of the supported catalyst prepared in example 92. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 100° C. The reactor was rapidly pressurized to 90 psigethylene and the temperature ramped up to 140° C. After 60 minutes at140° C., the reaction was quenched by the addition of acetone, 6M HCland methanol. The swollen polyethylene was isolated by filtration anddried for several hours in a vacuum oven at 100° C. GPC: M_(n)=56,000;Mw/Mn=7.19.

Example 100

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-diisopropylphenylimino)-[1,4]dithiane prepared in Example 95

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of the supported catalyst prepared in example 95. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 50° C. The reactor was rapidly pressurized to 90 psigethylene. After 30 minutes at 50° C., the reaction was quenched by theaddition of acetone, 6M HCl and methanol. The swollen polyethylene wasisolated by filtration and dried for several hours in a vacuum oven at100° C. resulting in 1.25 g of a white rubbery solid (18,000 TO/h). ¹HNMR: 62 branches/1000 carbon atoms. GPC: M_(n)=336,000; Mw/Mn=2.22.

Example 101

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 93

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of the supported catalyst prepared in example 93. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 50° C. The reactor was rapidly pressurized to 90 psigethylene. After 60 minutes at 50° C., the reaction was quenched by theaddition of acetone, 6M HCl and methanol. The swollen polyethylene wasisolated by filtration and dried for several hours in a vacuum oven at100° C. resulting in 2.13 g of a white rubbery solid (30,000 TO/h). DSC:2^(nd) heat showed an endothermic maximum at 120° C. ¹H NMR: 17branches/1000 carbon atoms. GPC: Mn=119,000; Mw/Mn=2.93.

Example 102

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 94

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of the supported catalyst prepared in example 94. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 50° C. The reactor was rapidly pressurized to 90 psigethylene. After 60 minutes at 50° C., the reaction was quenched by theaddition of acetone, 6M HCl and methanol. The swollen polyethylene wasisolated by filtration and dried for several hours in a vacuum oven at100° C. resulting in 5.97 g of a white rubbery solid (41,000 TO/h). DSC:2^(nd) heat showed an endothermic maximum at 120° C. GPC: Mn=138,000;MwMn=2.95. ¹H NMR: 17 branches/1000 carbon atoms.

Example 103

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared according to theprocedure described in Example 92

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of supported catalyst. Upon removing the autoclave from the box, 150mL of toluene was added and the reactor was heated to 65° C. The reactorwas rapidly pressurized to 100 psig ethylene. After 60 minutes at 65°C., the reaction was quenched by the addition of acetone, 6M HCl andmethanol. The swollen polyethylene was isolated by filtration and driedfor several hours in a vacuum oven at 100° C. resulting in 9.0 g of awhite rubbery solid (62,000 TO/h). DSC: 2^(nd) heat showed anendothermic maximum at 116° C. GPC: M_(n)=83,500; Mw/Mn=4.71. ¹H NMR: 35branches/1000 carbon atoms.

Example 104

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 96

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of the supported catalyst prepared in example 96. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 50° C. The reactor was rapidly pressurized to 100 psigethylene. After 60 minutes at 50° C., the reaction was quenched by theaddition of acetone, 6M HCl and methanol. The swollen polyethylene wasisolated by filtration and dried for several hours in a vacuum oven at100° C. resulting in 6.5 g of a white rubbery solid (88,000 TO/h). DSC:2^(nd) heat showed a broad melt transition with an endothermic maximumat 119° C. GPC: Mn=182,600; Mw/Mn=3.01. ¹H NMR: 19 branches/1000 carbonatoms.

Example 105

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 96

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of the supported catalyst prepared in example 96. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 50° C. The reactor was rapidly pressurized to 100 psigethylene. After 60 minutes at 50° C., the reaction was quenched by theaddition of acetone, 6M HCl and methanol. The swollen polyethylene wasisolated by filtration and dried for several hours in a vacuum oven at100° C. resulting in 5.4 g of a white rubbery solid (74,000 TO/h). DSC:2^(nd) heat showed abroad melt transition with an endothermic maximum at120° C. GPC: Mn=186,500; Mw/Mn=2.66. ¹H NMR: 18 branches/1000 carbonatoms.

Example 106

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared in Example 96

A 600 mL Parr® autoclave was first heated to about 100° C. under dynamicvacuum to ensure the reactor was dry. The reactor was then purged withargon. The 600 mL Parr® autoclave was charged in the glove box with 100mg of the supported catalyst prepared in example 96. Upon removing theautoclave from the box, 150 mL of toluene was added and the reactor washeated to 30° C. The reactor was rapidly pressurized to 100 psigethylene. After 60 minutes at 30° C., the reaction was quenched by theaddition of acetone, 6M HCl and methanol. The swollen polyethylene wasisolated by filtration and dried for several hours in a vacuum oven at100° C. resulting in 11.5 g of a white rubbery solid (160,000 TO/h).DSC: 2^(nd) heat showed an endothermic maximum at 127° C. GPC:Mn=279,000; Mw/Mn=2.73. ¹H NMR: 7 branches/1000 carbon atoms.

Example 107 Synthesis of the supported nickel complex of2,3-bis(phenylimino)-[1.4]dithiane

A 500 mL flame-dried pear-shaped flask equipped with a magnetic stir barand capped by a septum was charged with 27 mg (52 mol) of the nickeldibromide complex of 2,3-bis(phenylimino)-[1,4]dithiane and 1.0 g of MAOtreated silica (Witco TA 02794/HL/04). The solid mixture was cooled to0° C. in an ice bath and 25 mL of dry, deoxygenated CH₂Cl₂ was added.The reaction was stirred at 0° C. for 50 min, then the volatiles wereremoved by evaporation under reduced pressure (0.2 torr) at 0° C. for 40min to afford the supported catalyst as a light green-grey powder whichwas stored under nitrogen at −25° C.

Example 108 Synthesis of the supported nickel complex of2,3-bis(2-tert-butylphenylimino)-[1.4]dithiane

A 500 mL flame-dried pear-shaped flask equipped with a magnetic stir barand capped by a septum was charged with 34 mg (56 mol) of the nickeldibromide complex of 2,3-bis(2-tert-butylphenylimino)-[1,4]dithiane and1.0 g of MAO treated silica (Witco TA 02794/HL/04). The solid mixturewas cooled to 0° C. in an ice bath and 25 mL of dry, deoxygenated CH₂Cl₂was added. The reaction was stirred at 0° C. for 50 min, then thevolatiles were removed by evaporation under reduced pressure (0.2 torr)at 0° C. for 40 min to afford the supported catalyst as a light brownpowder which was stored under nitrogen at −25° C.

Example 109 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane

A 500 mL flame-dried pear-shaped flask equipped with a magnetic stir barand capped by a septum was charged with 30 mg (55 mol) of the nickeldibromide complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane and1.01 g of MAO treated silica (Witco TA 02794/HL/04). The solid mixturewas cooled to 0° C. in an ice bath and 25 mL of dry, deoxygenated CH₂Cl₂was added. The reaction was stirred at 0° C. for 65 min, then thevolatiles were removed by evaporation under reduced pressure (0.2 torr;20 min at 0° C., 75 min at 25° C.) to afford the supported catalyst as abrown powder which was stored under nitrogen at −25° C.

Example 110

Polymerization of ethylene using the supported nickel complex of2,3-bis(phenylimino)-[1,4]dithiane

A 500 mL flame-dried pear-shaped flask equipped with a magnetic stir barand capped by a septum was charged with 100 mg of the supported nickelcomplex of 2,3-bis(phenylimino)-[1,4]dithiane prepared in Example 107.The flask was evacuated and refilled with ethylene, then treated with 50mL of dry, deoxygenated toluene and stirred under 1 atm ethylene at 23°C. for 14 h. The reaction was quenched by the addition of methanol,acetone and 6 N HCl. The polymer which separated was isolated byfiltration and dried in vacuo to afford 0.177 g of white, powderypolyethylene. DSC: (2nd heat) melt endothermic maxima at ca. 100, 106and 127° C. GPC: M_(n)=1,100 g/mol; M_(w)/M_(n)=15.5.

Example 111

Polymerization of ethylene using the supported nickel complex of2,3-bis(2-tert-butylphenylimino)-[1,4]dithiane

A 500 mL flame-dried pear-shaped flask equipped with a magnetic stir barand capped by a septum was charged with 100 mg of the supported nickelcomplex of 2,3-bis(2-tert-butylphenylimino)-[1,4]dithiane prepared inExample 108. The flask was evacuated and refilled with ethylene, thentreated with 50 mL of dry, deoxygenated toluene and stirred under 1 atmethylene at 23° C. for 125 min. The reaction was quenched by theaddition of methanol, acetone and 6 N HCl. The polymer which separatedwas isolated by filtration and dried in vacuo to afford 0.529 g ofwhite, powdery polyethylene. DSC: (2nd heat) melt endothermic maxima at96 and 110° C. ¹H NMR (o-dichlorobenzene): 36 branches/1000 carbonatoms. GPC: M_(n)=120,000; M_(w)/M_(n)=2.46.

Example 112

Polymerization of ethylene using the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1.4]dioxane

A 500 mL flame-dried pear-shaped flask equipped with a magnetic stir barand capped by a septum was charged with 106 mg of the supported nickelcomplex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dioxane prepared inExample 109. The flask was evacuated and refilled with ethylene, thentreated with 50 mL of dry, deoxygenated toluene and stirred under 1 atmethylene at 23° C. for 255 min. The reaction was quenched by theaddition of methanol, acetone and 6 N HCl. The polymer which separatedwas isolated by filtration and dried in vacuo to afford 3.2 g of white,powdery polyethylene. ¹H NMR (o-dichlorobenzene): 20 branches/1000carbon atoms. DSC: (2nd heat) melt endothermic maximum at 118° C. GPC:M_(n)=150,000; M_(w)/M_(n)=3.10.

Example 113 Copolymerization of ethylene and ethyl undecenoate using thesupported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared as described inExample 92

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 100 mg of the nickel/MAO treated silica supportedcatalyst system. The flask was placed under an ethylene atmosphere, and45 mL of toluene and 2.5 mL of ethyl undecenoate was added, giving apurple suspension. The polymerization was left to stir for 5 hours at 0°C. After 5 hours at 0° C., the reaction was quenched by the addition ofacetone, 6M HCl and methanol. The white copolymer was isolated byfiltration, washed with copious amounts of acetone and dried for severalhours in a vacuum oven at 100° C. resulting in 1.3 g of a white powderysolid (1800 TO/h based on 100% active catalyst). ¹H NMR indicates 1 wt %of ethyl undecenoate incorporated into the copolymer.

Example 114 Copolymerization of ethylene and ethyl undecenoate using thesupported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane prepared as described inExample 92

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 100 mg of the nickel/MAO treated silica supportedcatalyst system. The flask was placed under an ethylene atmosphere, 45mL of toluene and 2.5 mL of ethyl undecenoate was added giving a purplesuspension. The polymerization was left to stir for 3.5 hours at 23° C.After 3.5 hours at 23° C., the reaction was quenched by the addition ofacetone, 6M HCl and methanol. The white copolymer was isolated byfiltration, washed with copious amounts of acetone and dried for severalhours in a vacuum oven at 100° C. resulting in 1.4 g of a white powderysolid (2700 TO/h based on 100% active catalyst). ¹H NMR indicates 1 wt %ethyl undecenoate incorporated into the copolymer.

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

Example 115 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 9 mg (16 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 3 g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 25 ml of toluene was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour, thesolvent was removed in vacuo giving 2.8 g of supported catalystmaterial.

Example 116 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 6 mg (10 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and I g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 20 ml of CH₂Cl₂was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour, thesolvent was removed in vacuo giving a brown supported catalyst material.The supported catalysts was then suspended in 20 ml of hexane followedby addition of 2 ml (4 mmol) of trimethylaluminum (TMA). The mixture wasstirred at 0° C. for one hour. The solvent was removed in vacuo alongwith excess TMA leaving the supported catalyst system.

Example 117 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 15 mg (26 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of silica (GraceDavison XPO-2402). The solid mixture was cooled to 0° C. in an ice bathand 20 ml of toluene and 7 ml of a MAO solution in toluene was added.The reaction was rapidly stirred at 0° C. for 1 hour. After 1 hour, thesolvent was removed in vacuo giving 1.3 g of supported catalyst.

Example 118 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenyl imino)-[1,4]-dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 18 mg (31 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 3 g of MAO treatedsilica (purchased from Witco TA 02794/HL/04). The solid mixture wascooled to 0° C. in an ice bath and 25 ml of CH₂Cl₂was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour, thesolvent was removed in vacuo giving a brown supported catalyst material.The supported catalysts was then suspended in 20 ml of hexane followedby addition of 0.5 ml of MAO The mixture was stirred at 0° C. for onehour. The solvent was removed in vacuo leaving 2.9 g of the supportedcatalyst.

Example 119 Synthesis of the supported nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane

A flame dried pear-shaped flask equipped with a stir bar and a septumwas charged with 6 mg (10 μmol) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of silica (GraceDavison XPO-2402). The solid mixture was cooled to 0° C. in an ice bathand 20 ml of hexane and 2 ml of a TMA solution in toluene was added. Thereaction was rapidly stirred at 0° C. for 1 hour. After 1 hour, thesolvent was removed in vacuo giving 0.94 g of supported catalyst.

Gas Phase Polymerization

Catalysts Preparation

A—XXVII/MAO on Silica (Witco)/0.3 mg of XXVII per gram silica. Seeexample 115 as a representative example.

B—XXVII/MAO on Silica (Witco)/3 mg of XXVII per gram silica. See example92 as a representative example.

C—XXVII/MAO on Silica (Witco)/0.3 mg of XXVII per gram silica/extra MAOadded. See example 118 as a representative example.

D—XXVII/Silica (Grace Davison XPO-2402)/MAO solution/1.5 mg of XXVII pergram silica. See example 117 as a representative example.

E—XXVII/MAO on Silica (Witco)/0.6 mg of XXVII per gram silica/extra MAOadded. See example 118 as a representative example.

F—XXVII/MAO on Silica (Witco)/0.6 mg of XXVII per gram silica/extra TMAadded. See example 116 as a representative example.

G—XXVII/Silica (Grace Davison XPO-2402)/TMA solution/0.6 mg of XXVII pergram silica. See example 117 as a representative example.

H—XXVII/MAO on Silica (Witco)/0.6 mg of XXVII per gram silica. Seeexample 115 as a representative example.

Gas Phase Polymerization Procedure

The basic procedure involves loading a 600 ml Parr® stirred autoclavewith 300 g of NaCl (dried in a vacuum oven at 100° C. for 24 hours) anda known amount of supported XXVII catalyst. The ethylenehomopolymerization reactions summarized below were run between 50° C.and 80° C. and 100 and 1000 psig ethylene. The resulting polyethylenewas isolated by dissolving the NaCl in a blender and collecting theremaining polymer by filtration. The polyethylene was washed with 6MHCl, water and actetone. The polymer was then dried in a vacuum oven at100° C.

A—80° C./800 psig ethylene/20 min reaction time/200 mg of supportedcatalyst.

B—65° C./400 psig ethylene/60 min reaction time/200 mg of supportedcatalyst.

C—65° C./200 psig ethylene/60 min reaction time/200 mg of supportedcatalyst.

D—65° C./100 psig ethylene/60 min reaction time/200 mg of supportedcatalyst.

E—80° C./100 psig ethylene/60 min reaction time/200 mg of supportedcatalyst.

F—80° C./200 psig ethylene/60 min reaction time/200 mg of supportedcatalyst.

G—80° C./400 psig ethylene/60 min reaction time/200 mg of supportedcatalyst.

H—80° C./400 psig ethylene/60 min reaction time/100 mg of supportedcatalyst.

I—80° C./100 psig ethylene/60 min reaction time/50 mg of supportedcatalyst.

J—80° C./100 psig ethylene/60 min reaction time/100 mg of supportedcatalyst.

K—100° C./100 psig ethylene/60 min reaction time/100 mg of supportedcatalyst.

L—80° C./200 psig ethylene/60 min reaction time/100 mg of supportedcatalyst.

M—100° C./200 psig ethylene/60 min reaction time/100 mg of supportedcatalyst.

N—100° C./400 psig ethylene/60 min reaction time/100 mg of supportedcatalyst.

O—80° C./200 psig ethylene/15 min reaction time/100 mg of supportedcatalyst.

P—80° C./200 psig ethylene/30 min reaction time/100 mg of supportedcatalyst.

Gas Phase Polymerization (Part 1) Mass Poly- Branches/ Exam- Cata- Pro-mer Total 1000C T_(m) ple lyst cedure (g) TO M_(n) PDI (¹HNMR) (° C.)120 A A 11.5 395K 164K 3.21 8 128 121 A B 8.5 293K 174K 3.59 9 124 122 AC 6.5 224K 124K 4.14 14 120 123 A D 4.7 160K 126K 4.01 21 117 124 A E3.5 121K  91K 3.67 28 119 125 A F 4.3 110K  94K 3.33 27 118 126 A G 9.8336K 121K 3.51 13 121 127 H B 13.5 231K 133K 3.22 10 122 128 H G 12 206K117K 3.39 13 121 129 H E 9.4 161K 106K 3.57 26 115 130 H H 7.8 267K 195K3.16 9 123 131 B E 14  48K  60K 4.42 48 114 132 B I 3  41K  94K 3.2 36114 133 B J 6.8  47K  88K 3.49 36 119 134 C J 9  61K  89K 3.94 34 119135 B K 4.4  30K  48K 4.14 53 113 136 C K 5.6  38K  63K 3.63 45 116 137B L 8  55K  93K 3.57 28 118 138 C L 12  82K  91K 3.79 30 119 Gas PhasePolymerization (Part 2) Mass Poly- Branches/ Exam- Cata- Pro- mer Total1000C ple lyst cedure (g) TO M_(n) PDI (¹HNMR) T_(m) 139 B M 7  48K  57K4.61 43 115 140 C M 7  48K  79K 3.77 48 116 141 B H 13.8  94K 106K 3.8424 120 142 B H 12.7  87K  99K 3.63 26 120 143 D J 4  54K  69K 5.53 35112 144 D K 3  41K  45K 4.11 56 112 145 D L 5  68K 117K 3.48 28 115 146D M 3.6  50K  70K 3.74 37 115 147 D H 5  68K 107K 3.24 18 118 148 D N5.9  80K  76K 4.2 25 116 149 E J 3.8 129K  65K 4.86 36 113 150 E K 1.5 51K  43K 4.4 47 114 151 E L 4 137K  74K 4.6 28 119 152 F H 4.7 161K106K 3.77 14 120 153 G H 0.35  12K  81K 4.32 23 119 154 G H 0.25  9K 57K 5.64 27 118 155 F H 3.8 130K  94K 3.46 18 120 156 A O 1.8 123K  71K4.70 29 117 157 A P 2.1 145K  80K 4.09 33 117 158 A L 2.3 157K  78K 4.7230 117 159 B O 4.9  34K  58K 4.50 38 117

The polymer made in the gas phase in example 131 (10.57 grams) wasfractionated using supercritical propane by isothermal increasingpressure profiling and critical, isobaric, temperature rising elutionfractionation to give the following data. (See, B. Folie, et al.,“Fractionation of Poly(ethylene-co-vinyl acetate) in SupercriticalPropylene: Towards a Molecular Understanding of a ComplexMacromolecule”, J. Appl. Polym. Sci., 64,2015-2030, 1997, and publiclyavailable literature from Phasex Corporation, 360 Merrimack St.,Lawrence, Mass. 01843, and at www.Phasex.com):

Temperature Weight of Collected Fraction Branching T_(m) Fraction (° C.)(g) M_(n) PDI (¹H NMR) (° C.) 1 40 1.43  29,500 2.76 72.2 50 2 40-600.43  28,600 3.02 62.3 55 3 60-65 0.74  49,400 2.37 57.5 79 4 65-75 0.52 83,100 2.14 45.9 92 5 75-85 0.80  80,900 2.22 36.5 99 6 85-95 0.50 77,400 2.40 34.3 102 7  95-100 0.61  93,200 2.26 26.3 108 8 100-1100.47 116,000 2.15 19.3 117 9 110-140 0.41 125,000 2.23 16.7 122 10 140-150 0.15 184,000 2.96 14.3 124 residue — 3.85 — — <5 — Bulk — — 59,900 4.42 48 114 Sample

The polymer made in the gas phase in example 138 (12 grams) wasfractionated using supercritical propane by isothermal increasingpressure profiling and critical, isobaric, temperature rising elutionfractionation to give the following data. (See, B. Folie, et al.,“Fractionation of Poly(ethylene-co-vinyl acetate) in SupercriticalPropylene: Towards a Molecular Understanding of a ComplexMacromolecule”, J. Appl. Polym. Sci., 64, 2015-2030, 1997, and publiclyavailable literature from Phasex Corporation, 360 Merrimack St.,Lawrence, Mass. 01843, and at www.Phasex.com):

Temperature Weight of Collected Fraction Branching T_(m) Fraction (° C.)(g) M_(n) PDI (¹H NMR) (° C.) 1 40 0.38  20,500 3.12 71 64 2 40-65 0.60 30,200 3.10 57 70 3 65-75 0.73  43,600 2.73 47 87 4 75-85 0.82  49,9003.16 35 98 5 85-90 0.54  63,200 2.58 30 106 6 90-95 0.62  81,200 2.42 25109 7  95-100 0.60  79,700 2.51 22 114 8 100-105 0.89  77,900 3.04 18118 9 105-110 0.81 117,600 2.30 16 121 10  110-115 0.65 115,000 2.59 13124 11  115-120 0.39 116,500 2.61 11 126 12  120-125 0.16 139,500 2.4311 125 13  125-150 0.25 151,300 2.43 — 123 residue — 2.2 141,000 5.29 —— Bulk — 12  90,700 3.79 30 119 Sample

Solution Phase Polymerization

Solution Phase Polymerization Procedure

A 600 mL Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 mL of toluene and a stock solution (CH₂Cl₂) of the nickel dibromidecomplex of 2,3-bis(2,6-dimethyl-phenylimino)[1,4]-dithiane. Theautoclave was heated to the desired temperature and a cocatalyst wasadded. The reactor was rapidly pressurized to the desired pressure.After the desired reaction time, the polymerization was quenched by theaddition of acetone, and methanol. The swollen polyethylene whichseparated was isolated by filtration and dried for several hours in avacuum oven at 80° C. As used herein, Et₂AlCl refers to diethyl aluminumchloride.

A-cocatalyst=Et₂AlCl; mol cat.=8.7×10⁻⁷; solvent=mineral spirits;temperature=80° C.; ethylene pressure=600 psig; reaction time=20min.

B-cocatalyst=Et₂AlCl; mol cat.=8.7×10⁻⁷; solvent=mineral spirits;temperature=65° C.; ethylene pressure=600 psig; reaction time=20 min.

C-cocatalyst=Et₂AlCl; mol cat.=8.7×10⁻⁷; solvent=mineral spirits;temperature=65° C.; ethylene pressure=800 psig; reaction time=20 min.

D-cocatalyst=Et₂AlCl; mol cat.=17.5×10⁻⁷; solvent=toluene;temperature=80° C.; ethylene pressure=600 psig; reaction time=20 min.

E-cocatalyst=Et₂AlCl; mol cat.=17.5×10⁻⁷; solvent=toluene;temperature=75° C.; ethylene pressure=600 psig; reaction time=20 min.

F-cocatalyst=Et₂AlCl; mol cat.=17.5×10⁻⁷; solvent=toluene;temperature=75° C.; ethylene pressure=800 psig; reaction time=20 min.

G-cocatalyst=Et₂AlCl; mol cat.=17.5×10⁻⁷; solvent=toluene;temperature=80° C.; ethylene pressure=400 psig; reaction time=20 min.

H-cocatalyst=Et₂AlCl; mol cat.=17.5×10⁻⁷; solvent=toluene;temperature=65° C.; ethylene pressure=400 psig; reaction time=20 min.

I-cocatalyst=Et₂AlCl; mol cat.=17.5×10⁻⁷; solvent=toluene;temperature=100° C.; ethylene pressure=800 psig; reaction time=20 min.

Solution Phase Polymerization Mass Ex- Poly- Branches/ am- Pro- merTotal 1000C T_(m) ple Catalyst cedure (g) TO M_(n) PDI (¹HNMR) (° C.)160 XXVII A 6 247K  83K 2.42 33 94 161 XXVII B 9 370K 135K 2.61 26 113162 XXVII C 6 245K 144K 2.30 24 113 163 XXVII D 5.7 116K  66K 1.85 47 80164 XXVII E 6.3 129K  58K 2.18 44 75 165 XXVII F 7.8 159K  63K 2.43 3795 166 XXVII G 3.8  78K  52K 1.85 — 55 167 XXVII H 5.5 112K  78K 1.93 4578 168 XXVII I 1.5  31K  32K 1.85 63 55

Example 169

Preparation of MAO supported on silica (Grace Davison XPO-2402),MAO/2402

A 500-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith silica (Grace Davison XPO-2402; 3.08 g) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. Upon stirring, anhydrous toluene (80 mL) was then added,followed by 19.0 mL of a 10 wt % of MAO in toluene. The suspension washeated to 80° C. for 4 hours, cooled to room temperature and thentransferred via canula onto a filter funnel. The solid was washed withtoluene (3×50 mL) and dried in vacuo to give 3.64 g solid. BET surfacearea: 300.9 m² g⁻¹. Pore volume: 1.19 cm³ g⁻¹. Average Pore Diameter:157.3 Å. Obsd wt % Al: 6.8.

Example 170

Preparation of diethylaluminum chloride (DEAC) supported on silica(Grace Davison XPO-2402). DEAC/2402

A 500-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith silica (Grace Davison XPO-2402; 3.87 g) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. Upon stirring, anhydrous toluene (80 mL) was then added,followed by 20.0 mL of a 1.8 M of DEAC in toluene. The suspension washeated to 80° C. for 4 hours, cooled to room temperature and thentransferred via canula onto a filter funnel. The solid was washed withtoluene (5×50 mL) and dried in vacuo to give 4.21 g solid. BET surfacearea: 280 m² g⁻¹. Pore volume: 1.0 cm³ g⁻¹. Average Pore Diameter: 132Å. Obsd wt % Al: 2.7.

Example 171

Preparation of triethylaluminum (TEAL) supported on silica (GraceDavison XPO-2402), TEAL/2402

A 500-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith silica (Grace Davison XPO-2402; 6.15 g) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. Upon stirring, anhydrous toluene (50 mL) was then added,followed by 100 mL of a 1.9 mL of TEAL in toluene. The suspension washeated to 80° C. for 4 hours, cooled to room temperature and thentransferred via canula onto a filter funnel. The solid was washed withtoluene (1×50 mL +4×25 mL) and dried in vacuo to give 6.34 g solid.

Example 172

Preparation of DEAC supported on silica (Grace Davison Sylopol 2212),DEAC/2212

A 500-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith silica (Grace Davison Sylopol 2212; 3.08 g) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. Upon stirring, anhydrous toluene (80 mL) was then added,followed by 16 mL of a 10 wt % solution of MAO in toluene. Thesuspension was heated to 80° C. for 4 hours, cooled to room temperatureand then transferred via canula onto a filter funnel. The solid waswashed with toluene (1×50 mL+6×25 mL+1×50 mL) and dried in vacuo to give3.35 g solid. Obsd wt % Al: 2.6.

Example 173

Preparation of MAO supported on silica (Grace Davison Sylopol 2212),MAO/2212

A 500-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith silica (Grace Davison Sylopol 2212; 6.27 g) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. Upon stirring, anhydrous toluene (50 mL) was then added,followed by 54 mL of a 10 wt % solution of MAO in toluene. Thesuspension was heated to 80° C. for 5 hours, cooled to room temperatureand then transferred via canula onto a filter funnel. The solid waswashed with toluene (1×50 mL+4×25 mL) and dried in vacuo to give 6.88 gsolid.

Example 174

Preparation of the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane supported on MAO/2402,XXVIIIMAO/2402

A 50-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith MAO/2402 (1.62 mg) and the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane (46.7 mg; 81.2 μmol)under a nitrogen inert atmosphere. The flask was equipped with amagnetic stirring bar and a septum cap. The solid was cooled to 0° C.and dichloromethane (20 mL) was added under vigorous stirring. Thevolatiles were removed in vacuum. The residual solid was dried in vacuoto give 1.40 g.

Example 175

Preparation of the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane supported on DEAC/2402,XXVII/DEAC/2402

A 50-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith DEAC/2402 (637 mg) and the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane (18.0 mg; 31.3 μmol)under a nitrogen inert atmosphere. The flask was equipped with amagnetic stirring bar and a septum cap. The solid was cooled to 0° C.and dichloromethane (25 mL) was added under vigorous stirring. After 1hour, the mixture was filtered by canula. The residual solid was thenrinsed with 10 mL dichloromethane and filtered by canula a second time.The solid was dried in vacuo and stored at −30° C. Yield: 213.4 mg.Loading of Ni complex/g support: 43 μmol (based on Ni analysis) and 37μmol (based on S analysis). Ni complex:Al ratio: 22 (based on Nianalysis) and 26 (based on S analysis).

Example 176

Preparation of the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane supported on DEAC/2212,XXVII/DEAC/2212

A 100-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith DEAC/2212 (758 mg) and the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane (22.1 mg; 38.4 μmol)under a nitrogen inert atmosphere. The flask was equipped with amagnetic stirring bar and a septum cap. The solid was cooled to 0° C.and dichloromethane (25 mL) was added under vigorous stirring. After 1hour, the mixture was filtered by canula. The residual solid was thenrinsed with 10 mL dichloromethane and filtered by canula a second time.The solid was dried in vacuo and stored at −30° C. Yield: 718 mg.Loading of Ni complex/g support: 49 μmol (based on Ni analysis) and 34μmol (based on S analysis). Ni complex:Al ratio: 20 (based on Nianalysis) and 28 (based on S analysis).

Example 177 Treatment of the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane supported on DEAC/2212with trimethylaluminum (TMAL), TMAL/XXVII/DEAC/2212

A 200-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane supported on DEAC/2212,XXVII/DEAC/2212 (81.5 mg; 3.4 μmol Ni) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. The solid was cooled to 0° C. and toluene (25 mL) was addedunder vigorous stirring. After 15 min, the volatile materials wereremoved in vacuo at 0° C. The resulting solid was further used toevaluate activity towards ethylene polymerization.

Example 178 Treatment of the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane supported on DEAC/2212with MAO, MAO/XXVII/DEAC/2212

A 50-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith the nickel complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane -supported on DEAC/2212,XXVII/DEAC/2212 (113.6 mg; 4.8 μmol Ni) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. The solid was cooled to 0° C. and toluene (25 mL) was addedunder vigorous stirring. After 2 min, the suspension was transferred viacanula onto a filter funnel. The resulting solid was dried in vacuo (89mg) and used to evaluate activity towards ethylene polymerization.

Example 179

Polymerization of Ethylene Using XXVII/MAO/2402

A 50-mL pear-shaped flask was charged with 152.5 mg XXVII/MAO/2402 (38μmol Ni/g; 5.8 μmol) under a nitrogen inert atmosphere. The inertatmosphere was replaced by 1 atm ethylene and toluene (25 mL) was added.The suspension was stirred for 2 hours at room temperature. The reactionwas then quenched with acetone and 6M HCl. The mixture was filtered. Theresulting solid was collected and dried in vacuo at 100° C. to give626.5 mg (where 152.5 mg of XXVII/MAO/2402 was used): M_(n)=95.5K,M_(w)=467.7K, M_(w)/M_(n)=4.9; 27 branches/100° C. (by ¹H NMR);T_(m)=118° C.

Example 180

Polymerization of Ethylene Using XXVII/MAO/2402

A 1000-mL Parre stirred reactor was charged with 169.3 mg (38 μmol Ni/g;6.4 μmol Ni) under a nitrogen inert atmosphere. Toluene (250 mL) wasadded and the reactor pressurized with ethylene (800 psig). The mixturewas stirred at 40° C. for 60 min. The vessel was vented and the catalystquenched with methanol and 6 M HCl The mixture was filtered and thecollected solid dried in vacuo at 100° C. to give 18.60 g polymer.

Example 181

Polymerization of Ethylene Using XXVII/MAO/2402

A 200-mL pear-shaped flask was charged with 79.3 mg XXVII/MAO/2402 (38μmol Ni/g; 3.0 μmol) under a nitrogen inert atmosphere. The inertatmosphere was replaced by 1 atm ethylene and toluene (50 mL) was added,followed by 2.0 mL MAO (10 wt % in toluene). The suspension was stirredfor 11 min at room temperature and then quenched with methanol and 6MHCl. The mixture was filtered. The resulting solid was collected anddried in vacuo at 100° C. to give 643 mg.

M_(n)=100.5K, Mw=325.3K, M_(w)/M_(n)=3.2; 41 branches/100° C. (by ¹HNMR); T_(m)=83° C. (by DSC).

Example 182

Polymerization of Ethylene Using XXVII/MAO/2402

A 600-mL Parr® stirred reactor was charged with 72.1 mg XXVII/MAO/2402(38 μmol Ni/g; 2.7 μmol Ni) under a nitrogen inert atmosphere. Thereactor was then charged with 150 mL anhydrous toluene and heated to 50°C. I then added 2.0 mL of a 10 wt % solution of MAO in toluene. Thevessel was pressurized with 100 psig ethylene and further heated to 69°C. The slurry agitated for 45 min. The mixture was quenched at elevatedpressure by addition of methanol through an injection loop. The vesselwas depressurized and the mixture treated with 6M HCl. The polymer wasisolated by filtration and dried in vacuo at 100° C. to give 4.21 gpolymer. M_(n)=55.7K, M_(w)=651.5K, M_(w)/M_(n)=11.7; 32 branches/100°C. (by ¹H NMR); T_(m)=113° C. (by DSC).

Example 183

Polymerization of Ethylene Using XXVIIIMAO/2402

A 200-mL pear-shaped flask was charged with 57.5 mg XXVII/MAO/2402 (38μmol Ni/g; 2.2 μmol) and 645 mg of MAO-treated silica (purchased fromWitco TA 027941/HL/04). The nitrogen inert atmosphere was replaced by 1atm ethylene, and 50 mL anhydrous toluene was then added. The suspensionwas stirred for 1 hour at room temperature before being quenched withacetone and 6M HCl. The mixture was filtered and the collected soliddried in vacuo at 100° C. to give 478 mg. M_(n)=195.5K, M_(w)=840.5K,M_(w)/M_(n)=4.3; 16 branches/100° C.; T_(m)=116° C. (by DSC).

Example 184

Polymerization of Ethylene Using XXVII/MAO/2402

A 600-mL Parr® stirred reactor was charged with 65.0 mg XXVII/MAO/2402(38 μmol Ni/g; 2.5 μmol Ni), 170 mg solid MAO and 214 g sodium chlorideunder a nitrogen inert atmosphere. The reactor was heated to 60° C., andsubsequently pressurized with 100 psig ethylene. The mixture was furtherheated to 65° C. and stirred for an additional 45 min. The vessel wasvented and the solid mixed with water. The mixture was filtered and thesolid washed with water, 6M HCl and methanol. The collected polymer wasdried in vacuo at 100° C. to give 2.38 g polymer. M_(n)=65.7K,M_(w)=487.0K, M_(w)/M_(n)=7.4; 29 branches/100° C. (by ¹H NMR);T_(m)=118° C. (by DSC).

Example 185

Polymerization of Ethylene Using XXVII/DEAC/2402

A 200-mL pear-shaped flask was charged with 82 mg XXVII/DEAC/2402 (40μmol Ni/g; 3.3 μmol) under a nitrogen inert atmosphere. Toluene (30 mL)was added. The inert atmosphere was then replaced by 1 atm ethylene. Thesuspension was stirred for 2 hours at room temperature. The reaction wasthen quenched with acetone and 6M HCl. The mixture was filtered. Theresulting solid was collected and dried in vacuo at 100° C. to give 418mg. M_(n)=114.0K, M_(w)=264.7K, M_(w)/M_(n)=2.3; 65 branches/100° C. (by¹H NMR); T_(m)=110° C. (by DSC).

Example 186

Polymerization of Ethylene Using XXVII/DEAC/2402

A 600-mL Parre stirred reactor was charged with 80.2 mg (40 μmol Ni/g;3.2 μmol Ni) under a nitrogen inert atmosphere. Toluene (150 mL) wasadded and the reactor pressurized with ethylene (800 psig). The mixturewas stirred at 40° C. for 58 min. The vessel was vented and the catalystquenched with methanol and 6M HCl The mixture was filtered and thecollected solid dried in vacuo at 100° C. to give 0.56 g polymer.M_(n)=246.5K, M_(n)=524.4K, M_(w)/M_(n)=2.1; 9 branches/100° C. (by ¹HNMR); T_(m)=127° C. (by DSC).

Example 187

Polymerization of Ethylene Using XXVII/DEAC/2212

A 200-mL pear-shaped flask was charged with 89.1 mg XXVII/DEAC/2212 (42μmol Ni/g; 3.7 μmol) under a nitrogen inert atmosphere. The inertatmosphere was replaced by 1 atm ethylene and toluene (50 mL) was added,followed by 2.0 mL MAO (10 wt % in toluene). The suspension was stirredfor 10 min at room temperature. Temperature was controlled with a waterbath. The reaction was then quenched with acetone and 6M HCl. Themixture was filtered. The resulting solid was collected and dried invacuo at 100° C. to give 1.80 g. M_(n)=132.8K, M_(w)=272.1 K,M_(w)/M_(n)=2.0; 52 branches/100° C. (by ¹H NMR); T_(m)=57° C. (by DSC).

Example 188

Polymerization of Ethylene Using XXVII/DEAC/2212

A 200-mL pear-shaped flask was charged with 81.2 mg XXVII/DEAC/2212 (42μmol Ni/g; 3.4 μmol) under a nitrogen inert atmosphere. The inertatmosphere was replaced by 1 atm ethylene and toluene (50 mL) was added,followed by 2.0 mL DEAC (1.8 M in toluene). The suspension was stirredfor 6 min at room temperature. Temperature was controlled with a waterbath. The reaction was then quenched with acetone and 6M HCl. Themixture was filtered. The resulting solid was collected and dried invacuo at 100° C. to give 857 mg. M_(n)=179.2K, M_(w)=444.7K,M_(w)/M_(n)=2.5; 32 branches/100° C. (by ¹H NMR); T_(m)=110° C. (byDSC).

Example 189

Polymerization of Ethylene Using TMAL/XXVII/DEAC/2212

A suspension of TMAL/XXVII/DEAC/2212 (3.4 μmol Ni) in toluene (50 mL)was then prepared at 0° C. The reaction flask was evacuated andbackfilled with 1 atm ethylene. The mixture was stirred at roomtemperature for 2 hours and then quenched with methanol and 6M HCl. Themixture was filtered. The resulting solid was collected and dried invacuo at 100° C. to give 212 mg. M_(n)=215.9K, M_(w)=910.6K,M_(w)/M_(n)=4.2; 15 branches/100° C. (by ¹H NMR); T_(m) 117° C. (byDSC).

Example 190

Polymerization of Ethylene Using MAO/XXVII/DEAC/2212

A 200-mL pear-shaped flask was charged with MAO/XXVII/DEAC/2212 (2.9μmol) and toluene (50 mL) under a nitrogen inert atmosphere. The flaskwas evacuated and backfilled with 1 atm ethylene. The suspension wasstirred for 2.5 hours before it was quenched with methanol and 6 M HCl.The mixture was filtered and the collected solid dried at 100° C. togive 304 mg. M_(n)=59.9K, M_(w)=487.3K, M_(w)/M_(n)=8.1; T_(m)=125° C.(by DSC).

Example 191

Preparation of MAO supported on silica (Grace Davison XPO-2402) usingincipient wetness, MAO^(IW)/2402

A 50-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith silica (Grace Davison XPO-2402; 3.33 g) under a nitrogen inertatmosphere. The flask was equipped with a magnetic stirring bar and aseptum cap. While agitating the content of the flask, 4 mL of MAO(Aldrich, 10 wt % in toluene) was added dropwise. The flask was thenplaced in vacuo for 2 h, then stored at room temperature under nitrogenfor two days. The flask was then heated to 80° C. for 1 h and evacuated.MAO was further added in 4 mL fractions until a total of 24 mL of MAOhad been added. Volatiles were removed at room temperature under vacuumbetween each addition. After additions were complete, the solid wasfurther dried in vacuo for 90 min, yielding 4.80 g solid.

Example 192

Preparation of the nickel complex of2.3-bis(2.6-dimethylphenylimino)-[1.4]-dithiane supported onMAO^(IW)/2402 by incipient wetness impregnation,XXVII^(IW)/MAO^(IW)/2402

A 50-mL pear-shaped flask, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith MAO^(IW)/2402 (784.9 mg) and cooled to 0° C. A solution of thenickel complex of 2,3-bis(2,6-dimethylphenylimino)-[1,4]-dithiane indichloromethane (10.4 mg in 1.2 mL) was then added dropwise under anitrogen inert atmosphere. The solid readily turned purple. The solidwas dried in vacuo at 0° C. and stored at −30° C. Yield: 615 mg.Calculated Loading of Ni complex/g support: 23 μmol/g.

Example 193

Polymerization of Ethylene Using XXVII^(IW)/MAO^(IW)/2402

A 1000-mL Parr® stirred reactor was charged with 75.2 mgXXVII^(IW)/MAO^(IW)/2402 (5 μmol Ni/g; 0.38 μmol Ni) under a nitrogeninert atmosphere. Toluene (300 mL) was added and the reactor pressurizedwith ethylene (300 psig). The mixture was stirred at 30° C. for 60 min.The vessel was vented and the catalyst quenched with methanol and 6MHCl. The mixture was filtered and the collected solid dried in vacuo at100° C. to give 470.3 mg polymer. M_(n)=268.1K, M_(w)=832.1K,M_(w)/M_(n)=3.1; 3 branches/100° C. (by ¹H NMR); T_(m)=132° C.

Example 194 Treatment of XXVII^(IW)/MAO^(IW)/2402 with 1-Hexene byincipient wetness, Hexene^(IW)/XXVII^(IW)/MAO^(IW)/2402

A 20-mL scintillation vial, previously heated to 200° C. for severalhours and allowed to cool to room temperature under vacuum, was chargedwith XXVII^(IW)/MAO^(IW)/2402 (410.6 mg) and cooled to −30° C. 1-Hexene(0.5 mL) was then added dropwise with vigorous agitation. A fraction ofthe resulting solid was stored at −30° C. and another at roomtemperature.

Example 195

Polymerization of Ethylene Using Hexenew/XXVII^(IW)/MAO^(IW)/2402

Under a nitrogen inert atmosphere, a 1000-mL Parr® stirred reactor wascharged with 55.3 mg Hexene^(IW)/XXVII^(IW)/MAO^(IW)/2402 (12 μmol Ni/g;0.66 μmol Ni) that had been stored at room temperature for 28 days.Toluene (300 mL) was added and the reactor pressurized with ethylene(300 psig). The mixture was stirred at 30° C. for 55 min. The vessel wasvented and the catalyst quenched with methanol and 6M HCl. The mixturewas filtered and the collected solid dried in vacuo at 100° C. to give1.41 g polymer. M_(n)=347.0, M_(w)=1077.0, M_(w)/M_(n)=3.1; 5branches/100° C. (by ¹H NMR); T_(m)=134° C.

Example 196

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence ofEt₂AlCl

A 600-ml Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 ml of mineral spirits and 1 ml of Et₂AlCl. The autoclave was heatedto 80° C. and 2.0 ml of a stock solution (0.25 mg in 1 ml CH₂Cl₂) of thenickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane was added via ahigh-pressure sample loop. The reactor was rapidly pressurized to 600psig ethylene. After 20 minutes at 80° C., the reaction was quenched bythe addition of methanol. The swollen polyethylene was isolated byfiltration and dried for several hours in a vacuum oven at 80° C. 3.3 gof a white rubbery solid was isolated (405,000 TO/h). DSC: (2nd heat)melt with an endothermic maximum at 51° C. ¹H NMR: 45 branches/1000carbon atoms. GPC: M_(n)=60,900; M_(w)/M_(n)=1.90.

Example 197

Polymerization of ethylene with the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane in the presence ofEt₂AlCl

A 600 ml Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with150 ml of toluene and 2 ml of Et₂AlCl. The autoclave was heated to 75°C. and pressurized to 500 psig ethylene and 2.0 ml of a stock solution(0.25 mg in 1 ml CH₂Cl₂) of the nickel dibromide complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane was added via a highpressure sample loop. The reactor was rapidly pressurized to 600 psigethylene and the temperature ramped to 80° C. After 20 minutes at 80°C., the reaction was quenched by the addition of methanol. The swollenpolyethylene was isolated by filtration and dried for several hours in avacuum oven at 80° C. 3.0 g of a white rubbery solid was isolated(368,000 TO/h). DSC: (2nd heat) melt with an endothermic maximum at 77°C. ¹H NMR: 45 branches/1000 carbon atoms. GPC: M_(n)-52,300;M_(w)/M_(n)=2.18.

Example 198 Synthesis of the Ni[η³-(H₂CC(CO₂Me)CH₂)]complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane

A flame dried Schlenk flask equipped with a stir bar and a rubber septumwas charged with 75 mg [η³-(H₂CC(CO₂Me)CH₂) Ni (μ-Br)]₂ (0.159 mmol),293 mg (0.318mmol) sodium tetra[3,5-(trifluoromethylphenyl)] borate and113 mg (0.318 mmol)of 2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane Thesolid mixture was dissolved in 10 ml of Et₂O. The solution was stirredfor 3 hours at room temperature while under an argon atmosphere. After 2hours, the reaction mixture was filtered and the solvent removed invacuo giving the desired product (328 mg, 75% yield).[η³⁻-(H₂CC(CO₂Me)CH₂) Ni (μ-Br)]₂ was synthesized according to theprocedure described in Wilke, G. et. al. Angew. Chem., Int. ed. Engl.1966, 5, 151.

Example 199 Ethylene Polymerization using the Ni[η³-(H₂CC(CO₂Me)CH₂)]complex of 2, 3-bis(2 6-dimethylphenylimino)-[1,4]dithiane

A 600 ml Parr® autoclave was first heated to about 100° C. under highvacuum to ensure the reactor was dry. The reactor was cooled and purgedwith argon. Under an argon atmosphere, the autoclave was charged with200 mL of toluene and 2 ml of MAO (10% weight solution in toluene). Theautoclave was heated to 25° C. and pressurized to 100 psig ethylene and2.0 ml of a stock solution (1 mg in 1 ml toluene) of theNi[η³-(H₂CC(CO₂Me)CH₂)] complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane was added via a highpressure sample loop. The reactor was rapidly pressurized to 400 psigethylene. After 60 minutes at 25° C., the reaction was quenched by theaddition of methanol. The swollen polyethylene was isolated byfiltration and dried for several hours in a vacuum oven at 80° C. 1.1 gof a powdery white solid was isolated. DSC: (2nd heat) melt with anendothermic maximum at 133° C. ¹H NMR: 2 branches/1000 carbon atoms.

Example 200 Synthesis of the silica supported Ni[η³-(H₂CC(CO₂Me)CH₂)]complex of 2,3-bis(2.6-dimethylphenylimino)-[1,4]dithiane

A flame dried Schlenk flask equipped with a stir bar and a rubber septumwas charged with 30 mg (22 μmol) Ni[η³-(H₂CC(CO₂Me)CH₂)] complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane and 1 g of MAO treatedsilica (Witco TA02794/HL/04). The solid mixture was cooled to 0° C. and20 ml of CH₂Cl₂ was added to the flask and stirred for 45 minutes. After45 minutes, the solvent was removed in vacuo giving the supportedcatalyst.

Example 201 Ethylene Polymerization using the silica supportedNi[η³-(H₂CC(CO₂Me)CH₂)] complex of2,3-bis(2,6-dimethylphenylimino)-[1,4]dithiane

A 600 ml, Parr® stirred autoclave with 300 g of NaCl (dried in a vacuumoven at 100° C. for 24 hours) and 100 mg of the supported catalystprepared in example 200 was heated to 50° C. and pressurized rapidly to400 psig ethylene. The temperature ramped up to 60° C. and the gas phasepolymerization was agitated for 1 hour. After 1 hour, the reactor wasvented and the contents poured in to a beaker. The polyethylene thatresulted was isolated by dissolving the NaCl in a blender and collectingthe remaining polymer by filtration. The polyethylene was washed with 6MHCl, water and acetone. The polymer was then dried in a vacuum oven at100° C. giving 4.7 grams of free flowing polyethylene. DSC: (2nd heat)melt with an endothermic maximum at 122° C. ¹H NMR: 22 branches/1000carbon atoms.

What is claimed is:
 1. A polymer composition comprise of monomer unitsderived from ethylene and from 0.1 to 50 wt % of a comonomer of theformula CH₂═CH(CH₂)_(n)CO₂R¹, wherein R¹ is hydrogen, hydrocarbyl,substituted hydrocarbyl, fluoroalkyl or silyl, and n is an integerbetween 3 and 18; in addition to the branches attributable to theincorporation of said comonomer, alkyl branches are present in saidpolymer composition, wherein between 5 and 50 alkyl branches per 1000carbon atoms are present and the majority of alkyl branches are methylbranches.
 2. A composition comprising an ester containingsemicrystalline copolyethylene with 5 to 30 alkyl branches/1000 carbonatoms, wherein the majority of alkyl branches are methyl branches, and aaverage of from about 1 to 50 ester terminated branches per chainresulting from ester comonomer incorporation.
 3. A compositioncomprising an olefin containing semicrystalline copolyethylene with 5 to30 alkyl branches/1000 carbon atoms, wherein the majority of alkylbranches are methyl branches, and a average of from about 1 to 50 olefinterminated branches per chain resulting from linear diene comonomerincorporation.
 4. A polyolefin which when fractionated based onsolubility using supercritical propane by isothermal increasingprofiling and critical, isobaric, temperature rising elutionfractionation, into ten fractions between about 40 and about 140° C.,wherein a first fraction taken at about 40° C. has between about 40 andabout 100 branches per 1000 carbon atoms, wherein between about 50 toabout 90% are methyl branches, about 5 to about 15% are ethyl branches,about 1 to about 10% are propyl branches, about 0 to about 15% are butylbranches, and between about 5 and about 15% are pentyl or longerbranches; a second fraction taken between about 40-60° C. has betweenabout 30 and about 90 branches per 1000 carbon atoms, wherein betweenabout 50 to about 90% are methyl branches, about 5 to about 15% areethyl branches, about 1 to about 10% are propyl branches, about 0 toabout 15% are butyl branches, and between about 5 and about 15% arepentyl or longer branches; a third fraction taken between about 60-65°C. has between about 30 and about 80 branches per 1000 carbon atoms,wherein between about 50 to about 90% are methyl branches, about 5 tobout 15% are ethyl branches, about 1 to about 10% are propyl branches,about 0 to about 15% are butyl branches, and between about 5 to about15% are pentyl or longer branches; a fourth fraction taken between about65-75° C. has between a out 20 and about 60 branches per 1000 carbonatoms, wherein between about 50 to bout 90% are methyl branches, about 5to about 15% are ethyl branches, about 1 to about 10% are propylbranches, about 0 to about 15% are butyl branches, an between about 5 toabout 15% are pentyl or longer branches; a fifth fraction take betweenabout 75-85° C. has between about 10 and about 50 branches per 1000carbon atoms, wherein between about 50 to about 90% are methyl branches,about 5 to about 15% are ethyl branches, about 0 to about 10% are propylbranches, about 0 to about 15% are butyl branches, and between about 5to about 15% are pentyl or longer branches; a sixth fraction takenbetween about 85-95° C. has between about 10 and about 40 branches per1000 carbon atoms, wherein between about 50 to about 90% are methylbranches, about 5 to about 15% are ethyl branches, about 0 to about 10%are propyl branches, about 0 to about 15% are butyl branches, andbetween about 5 and about 15% are pentyl or longer branches; a seventhfraction taken between about 95-100° C. has between about 5 and about 35branches per 1000 carbon atoms, wherein between about 50 to about 90%are methyl ranches, about 5 to about 15% are ethyl branches, about 0 toabout 10% are propyl branches, about 0 to about 15% are butyl branches,and between about 0 and about 15% are pentyl or longer branches; aneighth fraction taken between about 100-110° C. has between about 0 andabout 25 branches per 1000 carbon atoms, wherein between about 50 toabout 90% are methyl branches, about 5 to about 15% are ethyl branches,about 0 to about 10% are propyl branches, about 0 to about 15% are butylbranches, and between about 0 and about 15% are pentyl or longerbranches; a ninth fraction taken between about 110-140° C. has betweenabout 0 and bout 30 branches per 1000 carbon atoms, wherein betweenabout 50 to about 90% are methyl branches, about 5 to about 15% areethyl branches, about 0 to about 10% are propyl branches, about 0 toabout 15% are butyl branches, and between about 0 to about 15% arepentyl or longer branches; a tenth fraction taken between about 140-150°C. has between about 0 and about 20 branches per 1000 carbon atoms,wherein between about 50 to about 90% are methyl branches, about 5 oabout 15% are ethyl branches, about 0 to about 10% are propyl branches,about 0 to about 15% are butyl branches, and between about 0 to about15% are pentyl or longer branches; and a tenth fraction has betweenabout 0 and about 20 branches per 1000 carbon atoms.
 5. The polymer ofclaim 4, wherein said polymer is derived from ethylene alone and hasgreater than 30 branches per 1000 carbon atoms and a melt transition(endothermic maximum) in the DSC of greater than about 110° C., andwherein the polymer is a free flowing polymer.